Process for the production of substituted nicotinic acid esters

ABSTRACT

The present invention relates to a process for the preparation of compounds of formula (I) wherein the substituents are as defined in claim  1,  by reaction of a compound of formula (II) wherein R 3  is C 1 -C 8 alkyl or C 3 -C 6 cycloalkyl and R 4  and R 05  are as defined for formula (I), with a compound of formula (II) wherein R, R 1 , R 2  and X 1 , are as defined for formula (I) in claim  1,  in an inert solvent in the presence of a proton source.

The present invention relates to a novel process for the preparation of 6-haloalkyl-3-nicotinic acid esters and also to novel enamine intermediates for use in that process.

6-Haloalkyl-3-nicotinic acid esters are valuable intermediates for the preparation of herbicides such as those described, for example, in WO 01/94339.

From Heterocycles, Vol. 48, No. 4, 1998, pages 779-785 it is known to prepare 6-trifluoro-3-nicotinic acid ethyl esters substituted by aryl in the 4-position, corresponding to formula A, by means of dehydrogenation and subsequent oxidation of the compound of formula B in accordance with the following scheme

As a result of the uneconomic multi-step procedure, that process is not well suited to the large-scale preparation of 6-haloalkyl-3-nicotinic acid ethyl esters.

According to Heterocycles, Vol. 46, 1997, pages 129-132, 6-trifluoro-3-nicotinic acid methyl esters substituted by phenyl or alkyl in the 2-position, corresponding to formula C,

can be prepared by reacting a compound of formula E with a compound of formula D in benzene and in the presence of trifluoroacetic acid. In addition to unsatisfactory yields, that process has the serious disadvantage for large-scale preparation that the quality of the enamine (E) used as starting material continuously deteriorates during storage as a result of polymerisation reactions, making it considerably more difficult to ensure a consistent product quality.

The problem of the present invention is consequently to make available a novel process for the preparation of 6-haloalkyl-3-nicotinic acid esters which makes it possible to prepare those compounds at reasonable cost, in high yields and with good quality.

The present invention accordingly relates to a process for the preparation of compounds of formula I

wherein

R is C₁-C₆alkyl;

R₀₅ is Hydrogen, C₁-C₃alkyl, C₁-C₃haloalkyl or C₁-C₃alkyl-C₁-C₃alkoxy;

R₁ is a C₁-C₆alkylene, C₃-C₆alkenylene or C₃-C₆alkynylene chain which may be substituted one or more times by halogen and/or by R₅, the unsaturated bonds of the chain not being attached directly to the substituent X₁;

R₄ is C₁-C₄haloalkyl;

X₁ is oxygen, —O(CO)—, —(CO)O—, —O(CO)O—, —N(R₆)—O—, —O—NR₁₇—, thio, sulfinyl, sulfonyl, —SO₂NR₇—, —NR₁₈SO₂—, —N(SO₂R_(18a))—, —N(R_(18b))C(O)— or —NR₈—;

R_(18a) is C₁-C₆alkyl;

R₂ is hydrogen or C₁-C₈alkyl, or is a C₁-C₈alkyl, C₃-C₆alkenyl or C₃-C₆alkynyl group which may be substituted one or more times by substituents selected from halogen, hydroxy, amino, formyl, nitro, cyano, mercapto, carbamoyl, C₁-C₆alkoxy, C₁-C₆alkoxycarbonyl, C₂-C₆alkenyl, C₂-C₆haloalkenyl, C₂-C₆alkynyl, C₂-C₆haloalkynyl, C₃-C₆cycloalkyl, halo-substituted C₃-C₆cycloalkyl, C₃-C₆alkenyloxy, C₃-C₆alkynyloxy, C₁-C₆haloalkoxy, C₃-C₆haloalkenyloxy, cyano-C₁-C₆alkoxy, C₁-C₆alkoxy-C₁-C₆alkoxy, C₁-C₆alkoxy-C₁-C₆alkoxy-C₁-C₆alkoxy, C₁-C₆alkylthio-C₁-C₆alkoxy, C₁-C₆alkylsulfinyl-C₁-C₆alkoxy, C_(1-C) ₆alkylsulfonyl-C₁-C₆alkoxy, C₁-C₆alkoxycarbonyl-C₁-C₆alkoxy, C₁-C₆alkylcarbonyl, C₁-C₆alkylthio, C₁-C₆alkylsulfinyl, C₁-C₆alkylsulfonyl, C₁-C₆haloalkylthio, C₁-C₆haloalkylsulfinyl, C₁-C₆haloalkylsulfonyl, oxiranyl (which may in turn be substituted by C₁-C₆alkyl), (3-oxetanyl)oxy (which may in turn be substituted by C₁-C₆alkyl), benzyloxy, benzylthio, benzylsulfinyl, benzylsulfonyl, C₁-C₆alkylamino, di(C₁-C₆alkyl)amino, R₉S(O)₂O—, R₁₀N(R₁₁)SO₂—, rhodano, phenyl, phenoxy, phenylthio, phenylsulfinyl and phenylsulfonyl; it being possible for the phenyl- or benzyl-containing groups to be in turn substituted by one or more C₁-C₆alkyl, C₁-C₆haloalkyl, C₁-C₆alkoxy, C₁-C₆haloalkoxy, halogen, cyano, hydroxy or nitro groups, or

R₂ is phenyl which may be substituted one or more times by C₁-C₆alkyl, C₁-C₆haloalkyl, C₁-C₆alkoxy, C₁-C₆haloalkoxy, halogen, cyano, hydroxy or by nitro; or

R₂ is C₃-C₆cycloalkyl, C₁-C₆alkoxy- or C₁-C₆alkyl-substituted C₃-C₆cycloalkyl, 3-oxetanyl or C₁-C₆alkyl-substituted 3-oxetanyl; or

R₂ is a three- to ten-membered, monocyclic or fused bicyclic, ring system which may be aromatic, partially saturated or fully saturated and may contain from 1 to 4 hetero atoms selected from nitrogen, oxygen, sulfur, and/or may contain the group —C(═O)—, —C(═S)—, —C(═NR₁₉)—, —(N═O)—, —S(═O)— or —SO₂—, the ring system being attached to the substituent X₁ either directly or by way of a C₁-C₄alkylene, C₂-C₄alkenylene, C₂-C₄alkynylene, —N(R₁₂)—C₁-C₄alkylene, —O—C₁-C₄alkylene, —S—C₁-C₄alkylene, —SO—C₁-C₄alkylene or —SO₂—C₁-C₄alkylene group and each ring system containing no more than 2 oxygen atoms and no more than two sulfur atoms, and it being possible for each ring system itself to be substituted one or more times by C₁-C₆alkyl, C₁-C₆haloalkyl, C₂-C₆alkenyl, C₂-C₆haloalkenyl, C₂-C₆alkynyl, C₂-C₆haloalkynyl, C₁-C₆alkoxy, C₁-C₆haloalkoxy, C₃-C₆alkenyloxy, C₃-C₆alkynyloxy, mercapto, amino, hydroxy, C₁-C₆alkylthio, C₁-C₆haloalkylthio, C₃-C₆-alkenylthio, C₃-C₆haloalkenylthio, C₃-C₆alkynylthio, C₁-C₃alkoxy-C₁-C₃alkylthio, C₁-C₄alkyl-carbonyl-C₁-C₃alkylthio, C₁-C₄alkoxycarbonyl-C1-C₃alkylthio, cyano-C₁-C₃alkylthio, C₁-C₆-alkylsulfinyl, C₁-C₆haloalkylsulfinyl, C₁-C₆alkylsulfonyl, C₁-C₆haloalkylsulfonyl, aminosulfonyl, C₁-C₂alkylaminosulfonyl, N,N-di(C₁-C₂alkyl)aminosulfonyl, di(C₁-C₄alkyl)amino, halogen, cyano, nitro or by phenyl, it being possible for the phenyl group to be in turn substituted by hydroxy, C₁-C₆alkylthio, C₁-C₆haloalkylthio, C₃-C₆alkenylthio, C₃-C₆haloalkenylthio, C₃-C₆alkynylthio, C₁-C₃alkoxy-C₁-C₃alkylthio, C₁-C₄alkylcarbonyl-C₁-C₃alkylthio, C₁-C₄alkoxycarbonyl-C₁-C₃alkylthio, cyano-C₁-C₃alkylthio, C₁-C₆alkylsulfinyl, C₁-C₆-haloalkylsulfinyl, C₁-C₆alkylsulfonyl, C₁-C₆haloalkylsulfonyl, aminosulfonyl, C₁-C₂alkylaminosulfonyl, N,N-di(C₁-C₂alkyl)aminosulfonyl, di(C₁-C₄alkyl)amino, halogen, cyano or by nitro, and the substituents on nitrogen in a heterocyclic ring being other than halogen;

R₅ is hydroxy, C₁-C₆alkoxy, C₃-C₆cycloalkyloxy, C₁-C₆alkoxy-C₁-C₆alkoxy, C₁-C₆alkoxy-C₁-C₆alkoxy-C₁-C₆alkoxy or C₁-C₂alkylsulfonyloxy;

R₆, R₇, R₈, R₉, R₁₀, R₁₁, R₁₂, R₁₇, R₁₈ and R_(18b) are each independently of the others hydrogen, C₁-C₆alkyl, C₁-C₆haloalkyl, C₁-C₆alkoxycarbonyl, C₁-C₆alkylcarbonyl, C₁-C₆-alkoxy-C₁-C₆alkyl, C₁-C₆alkoxy-C₁-C₆alkyl substituted by C₁-C₆alkoxy, benzyl, or phenyl, it being possible for phenyl and benzyl to be in turn substituted one or more times by C₁-C₆alkyl, C₁-C₆haloalkyl, C₁-C₆alkoxy, C₁-C₆haloalkoxy, halogen, cyano, hydroxy or by nitro; R₆ not being hydrogen when R₉ is hydrogen, C₁-C₆alkoxycarbonyl or C₁-C₆alkylcarbonyl;

or the group —R₁—X₁—R₂ together is C₁-C₆alkyl, C₂-C₆alkenyl, C₂-C₆haloalkenyl, C₂-C₆-alkynyl, C₂-C₆haloalkynyl, C₃-C₆cycloalkyl, C₁-C₆alkoxy, C₁-C₆haloalkoxy, C₁-C₆alkylthio, C₁-C₆alkylsulfinyl, C₁-C₆alkylsulfonyl, C₁-C₆haloalkyl, C₁-C₆haloalkylthio, C₁-C₆haloalkylsulfinyl, C₁-C₆haloalkylsulfonyl, C₁-C₆alkoxycarbonyl, C₁-C₆alkylcarbonyl, C₁-C₆alkylamino, di(C₁-C₆alkyl)amino, C₁-C₆alkylaminosulfonyl, di(C₁-C₆alkyl)aminosulfonyl, —NH—S—R₁₃, —N—(C₁-C₄alkylthio)-R₁₃, —NH—SO—R₁₄, —N—(C₁-C₄alkylsulfonyl)-R₁₄, —NH—SO₂—R₁₅, —N—(C₁-C₄alkylsulfonyl)-R₁₅, nitro, cyano, halogen, hydroxy, amino, formyl, rhodano-C₁-C₆-alkyl, cyano-C₁-C₆alkyl, oxiranyl, C₃-C₆alkenyloxy, C₃-C₆alkynyloxy, C₁-C₆alkoxy-C₁-C₆-alkoxy, cyano-C₁-C₆alkenyloxy, C₁-C₆alkoxycarbonyloxy-C₁-C₆alkoxy, C₃-C₆alkynyloxy, cyano-C₁-C₆alkoxy, C₁-C₆alkoxycarbonyl-C₁-C₆alkoxy, C₁-C₆alkylthio-C₁-C₆alkoxy, C₁-C₆alkoxycarbonyl-C₁-C₆alkylthio, C₁-C₆alkoxycarbonyl-C₁-C₆alkylsulfinyl, C₁-C₆alkoxycarbonyl-C₁-C₆alkylsulfonyl, C₁-C₆alkylsulfonyloxy, C₁-C₆haloalkylsulfonyloxy, phenyl, benzyl, phenoxy, phenylthio, phenylsulfinyl, phenylsulfonyl, benzylthio, benzylsulfinyl or benzylsulfonyl, it being possible for the phenyl groups to be substituted one or more times by halogen, methyl, ethyl, trifluoromethyl, methoxy or by nitro;

or the group —R₁—X₁—R₂ together is a three- to ten-membered, monocyclic or fused bicyclic, ring system, which may be aromatic, partially saturated or saturated and which may contain from 1 to 4 hetero atoms selected from nitrogen, oxygen and sulfur and/or may contain one or two groups selected from —C(═O)—, —C(═S)—, —C(═NR₂₀)—, —(N═O)—, —S(═O)— and —SO₂—; the ring system either being attached to the pyridine ring directly via a carbon atom or being attached to the pyridine ring via a carbon atom or via a nitrogen atom by way of a C₁-C₄alkylene, C₂-C₄alkenyl or C₂-C₄alkynyl chain, and it being possible for each ring system to contain no more than 2 oxygen atoms and no more than two sulfur atoms, and it being possible for the ring system itself to be substituted one, two- or three times by substituents selected from C₁-C₆alkyl, C₁-C₆haloalkyl, C₃-C₆alkenyl, C₃-C₆haloalkenyl, C₃-C₆alkynyl, C₃-C₆haloalkynyl, C₃-C₆cycloalkyl, hydroxy, C₁-C₆alkoxy, C₁-C₆haloalkoxy, C₃-C₆alkenyloxy, C₃-C₆alkynyloxy, mercapto, C₁-C₆alkylthio, C₁-C₆haloalkylthio, C₃-C₆alkenylthio, C₃-C₆haloalkenylthio, C₃-C₆alkynylthio, C₁-C₃alkoxy-C₁-C₃alkylthio, C₁-C₃alkylcarbonyl-C₁-C₃alkylthio, C₁-C₄alkoxycarbonyl-C1-C₃alkylthio, cyano-C₁-C₃alkylthio, C₁-C₆alkylsulfinyl, C₁-C₆haloalkylsulfinyl, C₁-C₆alkylsulfonyl, C₁-C₆haloalkylsulfonyl, aminosulfonyl, C₁-C₂alkylaminosulfonyl, di(C₁-C₆alkyl)aminosulfonyl, C₁-C₃alkylene-R₁₆, amino, C₁-C₆alkylamino, C₁-C₆alkoxyamino, di(C₁-C₆alkyl)amino, (N—C₁-C₆alkyl)-C₁-C₆alkoxyamino, halogen, cyano, nitro, phenyl, benzyloxy and benzylthio, it being possible for phenyl, benzyloxy and benzylthio to be in turn substituted on the phenyl ring by C₁-C₃alkyl, C₁-C₃haloalkyl, C₁-C₃alkoxy, C₁-C₃haloalkoxy, halogen, cyano or by nitro, and substituents on a nitrogen atom in a heterocyclic ring being other than halogen;

R₁₃ is N(H)—C₁-C₆alkyl, N(H)—C₁-C₆alkoxy, N—(C₁-C₆alkyl)-C₁-C₆alkyl, N—(C₁-C₆alkyl)-C₁-C₆alkoxy, C₁-C₆alkoxy, C₁-C₆haloalkoxy, C₁-C₆alkyl, C₁-C₆haloalkyl, C₃-C₆alkenyl, C₃-C₆haloalkenyl, C₃-C₆alkynyl, C₃-C₆haloalkynyl, C₃-C₆cycloalkyl or phenyl, it being possible for phenyl to be in turn substituted by C₁-C₃alkyl, C₁-C₃haloalkyl, C₁-C₃alkoxy, C₁-C₃haloalkoxy, halogen, cyano or by nitro;

R₁₄ is N(H)—C₁-C₆alkyl, N(H)—C₁-C₆alkoxy, N—(C₁-C₆alkyl)-C₁-C₆alkyl, N—(C₁-C₆alkyl)-C₁-C₆alkoxy, C₁-C₆alkoxy, C₁-C₆haloalkoxy, C₁-C₆alkyl, C₁-C₆haloalkyl, C₃-C₆alkenyl, C₃-C₆haloalkenyl, C₃-C₆alkynyl, C₃-C₆haloalkynyl, C₃-C₆cycloalkyl or phenyl, it being possible for phenyl to be in turn substituted by C₁-C₃alkyl, C₁-C₃haloalkyl, C₁-C₃alkoxy, C₁-C₃haloalkoxy, halogen, cyano or by nitro;

R₁₅ is N(H)—C₁-C₆alkyl, N(H)—C₁-C₆alkoxy, N—(C₁-C₆alkyl)-C₁-C₆alkyl, N—(C₁-C₆alkyl)-C₁-C₆alkoxy, C₁-C₆alkoxy, C₁-C₆haloalkoxy, C₁-C₆alkyl, C₁-C₆haloalkyl, C₃-C₆alkenyl, C₃-C₆haloalkenyl, C₃-C₆alkynyl, C₃-C₆haloalkynyl, C₃-C₆cycloalkyl or phenyl, it being possible for phenyl to be in turn substituted by C₁-C₃alkyl, C₁-C₃haloalkyl, C₁-C₃alkoxy, C₁-C₃haloalkoxy, halogen, cyano or by nitro;

R₁₆ is C₁-C₃alkoxy, C₂-C₄alkoxycarbonyl, C₁-C₃alkylthio, C₁-C₃alkylsulfinyl, C₁-C₃alkylsulfonyl or phenyl, it being possible for phenyl to be in turn substituted by C₁-C₃alkyl, C₁-C₃haloalkyl, C₁-C₃alkoxy, C₁-C₃haloalkoxy, halogen, cyano or by nitro; and R₁₉ and R₂₀ are each independently of the other hydrogen, hydroxy, C₁-C₆alkyl, C₁-C₆haloalkyl, C₁-C₆alkoxy, cyano, C₁-C₆alkylcarbonyl, C₁-C₆alkoxycarbonyl or C₁-C₆alkylsulfonyl; which process comprises reacting a compound of formula II

wherein R₃ is C₁-C₈alkyl or C₃-C₆cycloalkyl and R₄ and R₀₅ are as defined for formula I, with a compound of formula III

wherein R, R₁, R₂ and X₁ are as defined for formula I, in an inert solvent in the presence of a proton source.

The alkyl groups appearing in the substituent definitions may be straight-chained or branched and are, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, pentyl, hexyl, heptyl and octyl and also the branched isomers thereof. Alkoxy, alkenyl and alkynyl groups are derived from the mentioned alkyl groups. The alkenyl and alkynyl groups may be mono- or poly-unsaturated.

Halogen is generally fluorine, chlorine, bromine or iodine, preferably fluorine or chlorine. The same is also correspondingly true for halogen in conjunction with other meanings such as haloalkyl or halophenyl.

Haloalkyl groups preferably have a chain length of from 1 to 6 carbon atoms. Haloalkyl is, for example, fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, 2,2,2-trifluoroethyl, 2-fluoroethyl, 2-chloroethyl, pentafluoroethyl, 1,1-difluoro-2,2,2-trichloroethyl, 2,2,3,3-tetrafluoroethyl or 2,2,2-trichloroethyl; preferably trichloromethyl, difluorochloromethyl, difluoromethyl, trifluoromethyl or dichlorofluoromethyl.

As haloalkenvl there come into consideration alkenyl groups substituted one or more times by halogen, halogen being fluorine, chlorine, bromine or iodine, especially fluorine or chlorine, for example 2,2-difluoro-1-methylvinyl, 3-fluoropropenyl, 3-chloropropenyl, 3-bromopropenyl, 2,3,3-trifluoropropenyl, 2,3,3-trichloropropenyl and 4,4,4-trifluoro-but-2-en-1-yl. Among the C₃-C₆alkenyl groups substituted once, twice or three times by halogen, preference is given to those that have a chain length of from 3 to 5 carbon atoms.

As haloalkynyl there come into consideration alkynyl groups substituted one or more times by halogen, halogen being bromine, iodine or, especially, fluorine or chlorine, for example 3-fluoropropynyl, 3-chloropropynyl, 3-bromopropynyl, 3,3,3-trifluoropropynyl and 4,4,4-trifluoro-but-2-yn-1-yl. Among the alkynyl groups substituted one or more times by halogen, preference is given to those that have a chain length of from 3 to 5 carbon atoms.

Alkoxy groups preferably have a chain length of from 1 to 6 carbon atoms. Alkoxy is, for example, methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy or tert-butoxy or the pentyloxy or hexyloxy isomers; preferably methoxy or ethoxy. Alkylcarbonyl preferably is acetyl or propionyl. Alkoxycarbonyl is, for example, methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl, n-butoxycarbonyl, isobutoxycarbonyl, sec-butoxycarbonyl or tert-butoxycarbonyl; preferably methoxycarbonyl or ethoxycarbonyl. Haloalkoxy groups preferably have a chain length of from 1 to 8 carbon atoms. Haloalkoxy is, for example, fluoromethoxy, difluoromethoxy, trifluoromethoxy, 2,2,2-trifluoroethoxy, 1,1,2,2-tetrafluoroethoxy, 2-fluoroethoxy, 2-chloroethoxy, 2,2-difluoroethoxy or 2,2,2-trichloroethoxy; preferably difluoromethoxy, 2-chlorethoxy or trifluoromethoxy. Alkylthio groups preferably have a chain length of from 1 to 8 carbon atoms. Alkylthio is, for example, methylthio, ethylthio, propylthio, isopropylthio, n-butylthio, isobutylthio, sec-butylthio or tert-butylthio, preferably methylthio or ethylthio. Alkylsulfinyl is, for example, methylsulfinyl, ethylsulfinyl, propylsulfinyl, isopropylsulfinyl, n-butylsulfinyl, isobutylsulfinyl, sec-butylsulfinyl or tert-butylsulfinyl; preferably methylsulfinyl or ethylsulfinyl.

Alkylsulfonyl is, for example, methylsulfonyl, ethylsulfonyl, propylsulfonyl, isopropylsulfonyl, n-butylsulfonyl, isobutylsulfonyl, sec-butylsulfonyl or tert-butylsulfonyl; preferably methylsulfonyl or ethylsulfonyl. Alkoxyalkoxy groups preferably have a chain length of from 1 to 8 carbon atoms. Examples of alkoxyalkoxy are: methoxymethoxy, methoxyethoxy, methoxypropoxy, ethoxymethoxy, ethoxyethoxy, propoxymethoxy and butoxybutoxy. Alkylamino is, for example, methylamino, ethylamino, n-propylamino, isopropylamino or the butylamine isomers. Dialkylamino is, for example, dimethylamino, methylethylamino, diethylamino, n-propylmethylamino, dibutylamino or diisopropylamino. Preference is given to alkylamino groups having a chain length of from 1 to 4 carbon atoms. Alkoxyalkyl groups preferably have a chain length of from 2 to 6 carbon atoms. Alkoxyalkyl is, for example, methoxymethyl, methoxyethyl, ethoxymethyl, ethoxyethyl, n-propoxymethyl, n-propoxyethyl, isopropoxymethyl or isopropoxyethyl. Alkylthioalkyl groups preferably have from 2 to 8 carbon atoms. Alkylthioalkyl is, for example, methylthiomethyl, methylthioethyl, ethylthiomethyl, ethylthioethyl, n-propylthiomethyl, n-propylthioethyl, isopropylthiomethyl, isopropylthioethyl, butylthiomethyl, butylthioethyl or butylthiobutyl. The cycloalkyl groups preferably-have from 3 to 8 ring carbon atoms, for example cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl. Phenyl, including phenyl as part of a substituent such as phenoxy, benzyl, benzyloxy, benzoyl, phenylthio, phenylalkyl and phenoxyalkyl, may be present in substituted form, in which case the substituents may be in the ortho-, meta- and/or para-position(s). Preferred substituent positions are the positions ortho and para to the ring attachment position.

In accordance with the process according to the invention there are preferably prepared those compounds of formula I wherein

R₄ is halomethyl or haloethyl;

R₀₅ is hydrogen;

X₁ is oxygen, —O(CO)—, —(CO)O—, —O(CO)O—, —N(R₆)—O—, —O—NR₁₇—, thio, sulfinyl, sulfonyl, —SO₂NR₇—, —NR₁₈SO₂— or —NR₈—;

R₂ is hydrogen or C₁-C₈alkyl, or a C₁-C₈alkyl, C₃-C₆alkenyl or C₃-C₆alkynyl group which is substituted one or more times by halogen, hydroxy, amino, formyl, nitro, cyano, mercapto, carbamoyl, C₁-C₆alkoxy, C₁-C₆alkoxycarbonyl, C₂-C₆alkenyl, C₂-C₆haloalkenyl, C₂-C₆-alkynyl, C₂-C₆haloalkynyl, C₃-C₆cycloalkyl, halo-substituted C₃-C₆cycloalkyl, or by C₃-C₆alkenyloxy, C₃-C₆alkynyloxy, C₁-C₆haloalkoxy, C₃-C₆haloalkenyloxy, cyano-C₁-C₆alkoxy, C₁-C₆alkoxy-C₁-C₆alkoxy, C₁-C₆alkoxy-C₁-C₆alkoxy-C₁-C₆alkoxy, C₁-C₆-alkylthio-C₁-C₆alkoxy, C₁-C₆alkylsulfinyl-C₁-C₆alkoxy, C₁-C₆alkylsulfonyl-C₁-C₆alkoxy, C₁-C₆-alkoxycarbonyl-C₁-C₆alkoxy, C₁-C₆alkoxycarbonyl, C₁-C₆alkylcarbonyl, C₁-C₆alkylthio, C₁-C₆alkylsulfinyl, C₁-C₆alkylsulfonyl, C₁-C₆haloalkylthio, C₁-C₆haloalkylsulfinyl, C₁-C₆-haloalkylsulfonyl, oxiranyl (which may in turn be substituted by C₁-C₆alkyl), or by (3-oxetanyl)oxy (which may in turn be substituted by C₁-C₆alkyl), or by benzylthio, benzylsulfinyl, benzylsulfonyl, C₁-C₆alkylamino, di(C₁-C₆alkyl)amino, R₉S(O)₂O—,

R₁₀N(R₁₁)SO₂—, rhodano, phenyl, phenoxy, phenylthio, phenylsulfinyl or by phenylsulfonyl; it being possible for the phenyl- or benzyl-containing groups to be in turn substituted by one or more C₁-C₆alkyl, C₁-C₆haloalkyl, C₁-C₆alkoxy, C₁-C₆haloalkoxy, halogen, cyano, hydroxy or nitro groups, or

R₂ is phenyl which may be substituted one or more times by C₁-C₆alkyl, C₁-C₆haloalkyl, C₁-C₆alkoxy, C₁-C₆haloalkoxy, halogen, cyano, hydroxy or by nitro; or

R₂ is C₃-C₆cycloalkyl, C₁-C₆alkoxy- or C₁-C₆alkyl-substituted C₃-C₆cycloalkyl, 3-oxetanyl or C₁-C₆alkyl-substituted 3-oxetanyl;

or R₂ is a five- to ten-membered, monocyclic or fused bicyclic, ring system which may be aromatic, partially saturated or fully saturated and may contain from 1 to 4 hetero atoms selected from nitrogen, oxygen, sulfur, and/or may contain the group —C(═O)—, —C(═S)—, —C(═NR₁₉)—, —(N═O)—, —S(═O)— or —SO₂—, the ring system being attached to the substituent X₁ directly or by way of a C₁-C₄alkylene, C₂-C₄alkenyl-C₁-C₄alkylene, C₂-C₄alkynyl-C₁-C₄alkylene, —N(R₁₂)—C₁-C₄alkylene, —SO—C₁-C₄alkylene or —SO₂—C₁-C₄alkylene group and each ring system containing no more than 2 oxygen atoms and no more than two sulfur atoms, and it being possible for each ring system itself to be substituted one or more times by C₁-C₆alkyl, C₁-C₆haloalkyl, C₂-C₆alkenyl, C₂-C₆haloalkenyl, C₂-C₆-alkynyl, C₂-C₆haloalkynyl, C₁-C₆alkoxy, C₁-C₆haloalkoxy, C₃-C₆alkenyloxy, C₃-C₆alkynyloxy, mercapto, amino, hydroxy, C₁-C₆alkylthio, C₁-C₆haloalkylthio, C₃-C₆alkenylthio, C₃-C₆haloalkenylthio, C₃-C₆alkynylthio, C₁-C₃alkoxy-C₁-C₃alkylthio, C₁-C₄alkylcarbonyl-C₁-C₃alkylthio, C₁-C₄alkoxycarbonyl-C₁-C₃alkylthio, cyano-C₁-C₃alkylthio, C₁-C₆alkylsulfinyl, C₁-C₆haloalkylsulfinyl, C₁-C₆alkylsulfonyl, C₁-C₆haloalkylsulfonyl, aminosulfonyl, C₁-C₂alkylaminosulfonyl, N,N-di(C₁-C₂alkyl)aminosulfonyl, di(C₁-C₄alkyl)amino, halogen, cyano, nitro or by phenyl, it being possible for the phenyl group to be in turn substituted by hydroxy, C₁-C₆alkylthio, C₁-C₆haloalkylthio, C₃-C₆alkenylthio, C₃-C₆haloalkenylthio, C₃-C₆alkynylthio, C₁-C₃alkoxy-C₁-C₃alkylthio, C₁-C₄alkylcarbonyl-C₁-C₃alkylthio, C₁-C₄-alkoxycarbonyl-C₁-C₃alkylthio, cyano-C₁-C₃alkylthio, C₁-C₆alkylsulfinyl, C₁-C₆haloalkylsulfinyl, C₁-C₆alkylsulfonyl, C₁-C₆haloalkylsulfonyl, aminosulfonyl, C₁-C₂alkylaminosulfonyl, N,N-di(C₁-C₂alkyl)aminosulfonyl, di(C₁-C₄alkyl)amino, halogen, cyano or by nitro, and the substituents on nitrogen in a heterocyclic ring being other than halogen;

R₆, R₇, R₈, R₉, R₁₀ R₁₁, R₁₂, R₁₇ and R₁₈ are each independently of the others hydrogen, C₁-C₆alkyl, C₁-C₆haloalkyl, C₁-C₆alkoxycarbonyl, C₁-C₆alkylcarbonyl, C₁ -C₆alkoxy-C₁-C₆alkyl, C₁-C₆alkoxy-C₁-C₆alkyl substituted by C₁-C₆alkoxy, benzyl, or phenyl, it being possible for phenyl and benzyl to be in turn substituted one or more times by C₁-C₆alkyl, C₁-C₆haloalkyl, C₁-C₆alkoxy, C₁-C₆haloalkoxy, halogen, cyano, hydroxy or by nitro; R₆ not being hydrogen when R₉ is hydrogen, C₁-C₆alkoxycarbonyl or C₁-C₆alkylcarbonyl;

or the group —R₁—X₁—R₂ together is C₁-C₆alkyl, C₂-C₆alkenyl, C₂-C₆haloalkenyl, C₂-C₆-alkynyl, C₂-C₆haloalkynyl, C₃-C₆cycloalkyl, C₁-C₆alkoxy, C₁-C₆haloalkoxy, C₁-C₆alkylthio, C₁-C₆alkylsulfinyl, C₁-C₆alkylsulfonyl, C₁-C₆haloalkyl, C₁-C₆haloalkylthio, C₁-C₆haloalkylsulfinyl, C₁-C₆haloalkylsulfonyl, C₁-C₆alkoxycarbonyl, C₁-C₆alkylcarbonyl, C₁-C₆alkylamino, di(C₁-C₆alkyl)amino, C₁-C₆alkylaminosulfonyl, di(C₁-C₆alkyl)aminosulfonyl, —NH—S—R₁₃, —N—(C₁-C₄alkylthio)-R₁₃, —NH—SO—R₁₄, —N—(C₁-C₄alkylsulfonyl)-R₁₄, —NH—SO₂—R₁₅, —N—(C₁-C₄alkylsulfonyl)-R₁₅, nitro, cyano, halogen, hydroxy, amino, formyl, rhodano-C₁-C₆alkyl; cyano-C₁-C₆alkyl, oxiranyl, C₃-C₆alkenyloxy, C₃-C₆alkynyloxy, C₁-C₆alkoxy-C₁-C₆alkoxy, cyano-C₁-C₆alkenyloxy, C₁-C₆alkoxycarbonyloxy-C₁-C₆alkoxy, C₃-C₆alkynyloxy, cyano-C₁-C₆alkoxy, C₁-C₆alkoxycarbonyl-C₁-C₆alkoxy, C₁-C₆alkylthio-C₁-C₆alkoxy, alkoxycarbonyl-C₁-C₆alkylthio, alkoxycarbonyl-C₁-C₆alkylsulfinyl, alkoxycarbonyl-C₁-C₆alkylsulfonyl, C₁-C₆alkylsulfonyloxy, C₁-C₆haloalkylsulfonyloxy, phenyl, benzyl, phenoxy, phenylthio, phenylsulfinyl, phenylsulfonyl, benzylthio, benzylsulfinyl or benzylsulfonyl, it being possible for the phenyl groups to be substituted one or more times by halogen, methyl, ethyl, trifluoromethyl, methoxy or by nitro;

or the group —R₁—X₁—R₂ together is a five- to ten-membered, monocyclic or fused bicyclic, ring system, which may be aromatic or partially saturated and which may contain from 1 to 4 hetero atoms selected from nitrogen, oxygen and sulfur, the ring system either being directly attached to the pyridine ring or being attached to the pyridine ring by way of a C₁-C₄alkylene group, and it being possible for each ring system to contain no more than 2 oxygen atoms and no more than two sulfur atoms, and/or to contain the group —C(═O)—, —C(═S)—, —C(═NR₂₀)—, —(N═O)—, —S(═O)— or —SO₂—;

and the ring system itself may be substituted one, two or three times by C₁-C₆alkyl, C₁-C₆-haloalkyl, C₃-C₆alkenyl, C₃-C₆haloalkenyl, C₃-C₆alkynyl, C₃-C₆haloalkynyl, C₁-C₆alkoxy, C₁-C₆haloalkoxy, C₃-C₆alkenyloxy, C₃-C₆alkynyloxy, mercapto, C₁-C₆alkylthio, C₁-C₆-haloalkylthio, C₃-C₆alkenylthio, C₃-C₆haloalkenylthio, C₃-C₆alkynylthio, C₂-C₅alkoxyalkylthio, C₃-C₅acetylalkylthio, C₃-C₆alkoxycarbonylalkylthio, C₂-C₄cyanoalkylthio, C₁-C₆alkylsulfinyl, C₁-C₆haloalkylsulfinyl, C₁-C₆alkylsulfonyl, C₁-C₆haloalkylsulfonyl, aminosulfonyl, C₁-C₂alkylaminosulfonyl, C₂-C₄dialkylaminosulfonyl, C₁-C₃alkylene-R₁₆, N(H)—C₁-C₆alkyl, N(H)—C₁-C₆alkoxy, N—(C₁-C₆alkyl)-C₁-C₆alkyl, N—(C₁-C₆alkyl)-C₁-C₆alkoxy, halogen, cyano, nitro, phenyl and by benzylthio, it being possible for phenyl and benzylthio to be in turn substituted on the phenyl ring by C₁-C₃alkyl, C₁-C₃haloalkyl, C₁-C₃alkoxy, C₁-C₃haloalkoxy, halogen, cyano or by nitro, and substituents on nitrogen in a heterocyclic ring being other than halogen; and

R₁₉ and R₂₀ are each independently of the other hydrogen, hydroxy, C₁-C₆alkyl, C₁-C₆-haloalkyl, C₁-C₆alkoxy, C₁-C₆alkylcarbonyl, C₁-C₆alkoxycarbonyl or C₁-C₆alkylsulfonyl.

The process according to the invention is especially suitable for the preparation of those compounds of formula I wherein R₁ is —CH₂—, —CH₂CH₂—, —CH₂CH₂CH₂—, —CF₂—, —CH═CHCH₂—, —CH(CH₃)— or —C≡CCH₂—, but preferably —CH₂—, the free valency on the left in each case being attached to the pyridine ring.

Preference is furthermore given to the preparation of those compounds of formula I wherein X₁ is oxygen, sulfonyl or a group —NR₁₈SO₂—, especially oxygen.

In accordance with the process according to the invention, special preference is given to the preparation of those compounds of formula I wherein R₂ is CH₃, CH₂CH₃, CH₂OCH₃, CH₂OCH₂CH₃, CH₂CH₂OCH₃, CH₂CH₂OCH₂CH₃, CH₂CF₃, propargyl, cyclopropylmethyl, benzyl, CH₂CH₂SO₂CH₃ or CH₂CH₂OCH₂CH₂OCH₃, but preferably CH₂CH₂OCH₃, with very special preference being given to those compounds wherein X₁ is oxygen and R₁ is —CH₂—.

In accordance with the process according to the invention, preference is given to the preparation of those compounds of formula I wherein R₀₅ is hydrogen, CH₃, CH₂Cl, CH₂Br or CH₂OCH₃, but especially hydrogen.

From that group, those compounds wherein R is ethoxy or methoxy may be prepared especially advantageously.

Furthermore, in accordance with the process according to the invention there may be advantageously prepared compounds of formula I wherein R₂ is

Where no free valency is indicated in those preferred meanings of R₂, as in the case of, for example,

the attachment position is at the carbon atom marked “CH”.

Furthermore, there may also be advantageously prepared those compounds wherein the group —R₁—X₁—R₂ together is a four- to ten-membered, monocyclic or fused bicyclic, ring system, which may be aromatic, partially saturated or saturated and contains from 1 to 4 hetero atoms selected from nitrogen, oxygen and sulfur and/or contains one or two groups selected from —C(═O)—, —C(═S)—, —C(═NR₂₀)— and —SO₂—, the ring system being attached to the pyridine ring via a carbon atom or preferably via a nitrogen atom by way of a C₁-C₄alkylene chain, especially a methylene chain. Among such ring systems special mention may be made of the following preferred, four- to seven-membered ring systems attached via a nitrogen atom to the methylene group, the attachment position being shown in each case at the bottom left:

wherein r is 0, 1 or 2; R₅₁, R₅₃, R₅₆ and R₆₅ are each independently of the others hydrogen, halogen, C₁-C₆alkyl, C₁-C₆haloalkyl, C₃-C₆cycloalkyl, C₃-C₆alkenyl, C₃-C₆alkynyl, C₁-C₃alkoxy-C₁-C₃alkyl, C₁-C₆alkoxy, C₃-C₆alkenyloxy, C₃-C₆alkynyloxy, C₁-C₆alkylthio, C₁-C₆alkylsulfinyl, C₁-C₆alkylsulfonyl, C₃-C₆alkenylthio or C₃-C₆alkynylthio; R₅₂ is hydrogen, C₁-C₆alkyl, C₁-C₆haloalkyl, C₃-C₆cycloalkyl, C₃-C₆alkenyl, C₃-C₆alkynyl, C₁-C₆alkoxy, amino, or phenyl which may in turn be substituted by R₇₀; R₅₄, R₅₅ and R₆₀ are each independently of the others hydrogen, C₁-C₆alkyl, C₁-C₆haloalkyl, C₃-C₆alkenyl, C₃-C₆alkynyl or C₃-C₆cycloalkyl; R₅₇, R₆₃, R₆₆, R₆₇, R₆₈ and R₆₉ are each independently of the others C₁-C₆alkyl, or phenyl which may in turn be substituted by R₇₀; R₆₄ is C₁-C₆alkyl, C₁-C₆haloalkyl, C₃-C₆cycloalkyl, C₃-C₆alkenyl, C₃-C₆alkynyl, or phenyl which may in turn be substituted by R₇₀; R₅₈ and R₆₁ are hydrogen, halogen, C₁-C₆alkyl or C₁-C₆haloalkyl; R₅₉ is C₁-C₆alkyl, C₁-C₆haloalkyl, C₁-C₃alkoxy-C₁-C₃alkyl, C₃-C₆alkenyl or C₃-C₆alkynyl; R₆₂ is hydrogen, C₁-C₆alkyl, C₁-C₄alkoxycarbonyl or C₁-C₄alkylthiocarbonyl; or R₅₁ together with R₅₂, or R₅₄ together with an adjacent group R₅₆, or R₅₈ together with an adjacent group R₅₉, or R₆₀ together with an adjacent group R₆₁, or, when r is 2, two adjacent groups R₅₆ or two adjacent groups R₆₁ together may form a saturated or unsaturated C₁-C₅alkylene or C₃-C₄alkenylene bridge, which may in turn be substituted by a group R₇₀ or interrupted by oxygen, sulfur or nitrogen; each R₇₀ is independently halogen, C₁-C₃alkyl, C₁-C₃haloalkyl, hydroxy, C₁-C₃alkoxy, C₁-C₃haloalkoxy, cyano or nitro; X is oxygen, sulfur or NR₆; X₃, X₄ and X₅ are oxygen or sulfur; X₆ and X₇ are oxygen, sulfur, S(O) or SO₂; and X₈ is CH₂, oxygen, sulfur, S(O), SO₂ or NR₇₁, wherein R₇₁ is hydrogen or C₁-C₆alkyl.

In the context of the present invention, preference is given to the group R₁—X₁—R₂ together being C₁-C₆alkyl, C₁-C₆haloalkyl, C₂-C₆alkenyl, C₂-C₆haloalkenyl, C₂-C₆alkynyl, C₂-C₆haloalkynyl, C₃-C₆cycloalkyl, C₁-C₆alkoxy or C₁-C₆alkylthio, e.g. methyl, ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, fluoromethyl, 2-fluoroethyl, difluoroethyl, trifluoroethyl, vinyl, 1-propenyl, methoxy, ethoxy, methylthio or ethylthio.

In the context of the present invention, preference is given to R being methyl, ethyl, n-propyl or isopropyl, especially ethyl.

R₃ is preferably methyl or ethyl, very especially ethyl.

R₄ is preferably trifluoromethyl, difluoromethyl, chlorodifluoromethyl, pentafluoroethyl, 2,2,2-trifluoroethyl, especially trifluoromethyl, chlorodifluoromethyl or difluoromethyl.

As inert solvents for the method according to the invention there are suitable, for example, aromatic solvents such as benzene, chlorobenzene, fluorobenzene, xylenes, toluene, or alcohols such as methanol or ethanol, and also ethyl acetate, acetonitrile, dimethyl sulfoxide, dimethylformamide, dimethylacetamide, N-methyl-2-pyrrolidone, acetone, butanone, halogenated solvents such as, for example, methylene chloride, trichloromethane, dichloroethylene or trichlorethane, ethers such as tetrahydrofuran, diethyl ether, 1,2-dimethoxyethane, dioxane or methyl tert-butyl ether. Ethanol and toluene are especially preferred.

Organic or mineral acids are suitable as the proton source. Examples of suitable proton sources are HCl, HBr, H₂SO₄, carboxylic acids such as acetic acid and derivatives thereof such as trifluoroacetic acid and trichloroacetic acid, sulfonic acids such as methanesulfonic acid or p-toluenesulfonic acid and also carbonic acid. As the proton source for the process according to the invention special preference is given to trifluoroacetic acid.

The reactions can be carried out at ambient temperature or at elevated temperature. In general, addition of the reactants is carried out at a temperature from ambient temperature to the boiling point of the solvent, especially from 20 to 140° C., preferably from 40 to 120° C., with subsequent heating of the reaction mixture, advantageously to the boiling point of the solvent.

The compounds of formula II are known or are accessible by known methods. Processes for the preparation of compounds of formula II are described, for example, in J. Org Chem. (1995) vol 95, 3523, in H. Amil, T. Kobayashi, H. Terasawa, K. Uneyama, Org. Lett. 3(20), 3103-3105 (2001) and also A. Colla, G. Clar, S. Krimmer, P. Fischer, M. A. P. Martins, Synthesis-Stuttgart (6),483-486 (1991).

Some of the compounds of formula III are known. The preparation of such compounds is described in H. G. O. Becker, J. Prakt. Chem. (1961), Vol 12, 294., in WO 00/24714 and also in D. H. Wu, W. Wang, J. Labelled Compd. Rad 39(2),105-107(1997).

The compounds of formula III wherein —R₁—X₁—R₂ is —CH₂—O—CH₂—CH₂—O—CH₃, that is to say compounds of formula IIIa

wherein R is as defined for formula III, are novel and were developed specifically for the preparation of compounds of formula I, and the present invention accordingly relates thereto. In a preferred compound of formula IIIa, R is methyl or ethyl.

Compounds of formula III can be prepared using processes known to the person skilled in the art, for example by reacting the unsaturated ketones on which they are based with ammonia gas as described in Preparation Example P1 hereinbelow.

In a preferred embodiment of the process according to the invention, the starting compounds of formula III are prepared from the 3-oxo-carboxylic acid esters on which they are based by introducing ammonia gas and then, without further isolation, reacting directly with the compounds of formula II. That process is especially advantageous for the large-scale preparation of compounds of formula I.

The compounds of formula I either may be used directly in the reaction mixture for further reactions or alternatively may be isolated. Isolation of the compounds of formula I can be carried out, for example, by extraction of the reaction mixture and subsequent removal of the solvent from the product-containing phase by customary methods.

The process according to the invention will be explained in greater detail in the following Preparation Examples:

EXAMPLE P1 Preparation of 3-amino-4-methoxyethoxy-but-2-enoic acid ethyl ester

A mixture of 1.37 g (6 mmol) of 3-oxo-4-methoxyethoxy-butanoic acid ethyl ester (1) in 13 ml of ethanol is introduced into a reaction vessel and cooled to a temperature of 0° C. using an ice/water bath.

Ammonia gas is then introduced for a period of 30 minutes, with stirring, and the reaction mixture is stirred for a further 20 minutes at a temperature of 0° C. After removing the cooling bath, the reaction mixture is allowed to warm up to a temperature of 20° C. and ammonia gas is then introduced for a further hour. The reaction mixture is then stirred for 20 hours.

After removal of the solvent in vacuo, there are obtained 1.3 g (95% of theory) of 3-amino-4-methoxyethoxy-but-2-enoic acid ethyl ester (2) in the form of an orange-coloured oil.

¹H NMR (CDCl₃): 1.30 (t, 3H, CH ₃CH₂O—), 3.40 (s, 3H, CH ₃O—), 3.55 (m, 2H, OCH ₂CH₂O), 3.60 (m, 2H, OCH₂CH ₂O), 4.10 (s, 2H, C═CCH ₂O—), 4.15 (q, 2H, CH₃CH ₂O—), 4.50 (s, 1H, CH═CNH₂).

¹³C NMR (CDCl₃): 14.7 (CH₃), 58.9 (CH₂), 59.2 (CH₃), 70.0 (CH₂), 71.0 (CH₂), 71.8 (CH₂), 81.9 (CH), 159.7 (C), 170.3 (C).

MS: 203 (M⁺), 158, 157,144,129, 114, 100, 98, 83, 71, 59, 45.

EXAMPLE P2 Preparation of 2-methoxyethoxymethyl-3-ethoxycarbonyl-6-trifluoromethyl-pyridine (4)

A mixture of 52.3 g (0.24 mol) of 3-oxo-4-methoxyethoxy-butanoic acid ethyl ester (1) in 150 ml of toluene is introduced into a reaction vessel equipped with a water separator.

Ammonia gas is then introduced into the reaction mixture for 2 hours, with stirring. Refluxing is then carried out for 30 minutes and the water is collected in the separator. After cooling the reaction mixture to a temperature of 20° C., the procedure is repeated. Ammonia gas is again introduced for 1.5 hours, with stirring, and the reaction mixture is then refluxed in order to separate off the water.

After cooling the reaction mixture, which contains 3-amino-4-methoxyethoxy-but-2-enoic acid ethyl ester (2), to a temperature of 20° C., 48 g (0.248 mol) of 1-ethoxy-3-oxo-4-trifluorobutene (3) are added and stirring is carried out at a temperature of 20° C. for 18 hours. 1.5 ml of trifluoroacetic acid are then added, stirring is carried out at a temperature of 20° C. for 2 hours and refluxing is carried out for a further 2 hours.

The reaction mixture is then allowed to cool down to a temperature of 20° C. and is then washed with 100 ml of 1M NaHCO₃. The aqueous phase is separated off and is then extracted with 150 ml of toluene and the combined organic phases are then dried over MgSO₄.

After removal of the solvent in vacuo, there are obtained 65.4 g (62% of theory) of 2-methoxyethoxymethyl-3-ethoxycarbonyl-6-trifluoromethylpyridine in the form of a dark-brown oil.

¹H NMR (CDCl₃): 1.40 (t, 3H, CH ₃CH₂O—), 3.35 (s, 3H, CH ₃O—), 3.55 (m, 2H, OCH ₂CH₂O), 3.70 (m, 2H, OCH₂CH ₂O), 4.45 (q, 2H, CH₃CH ₂O—), 5.00 (s, 2H, ArCH ₂O—), 7.70 (s,1H, ArH), 8.30 (s, 1H, ArH).

MS: 307 (M⁺), 262, 248, 233, 204, 202, 161, 128, 109, 59, 45

The other compounds listed in Table 1 can also be prepared in that manner.

In the following Table, the valency on the left of the radical R₁ is attached to the pyridine ring. When no free valency is indicated in the case of the substituent R₂, as in the case of, for example,

the attachment position is at the carbon atom marked “CH”. TABLE 1 Compounds of formula Ia (Ib)

wherein R is methyl or ethyl: Comp. no. R₄ R₁ R₂ X₁ A1  CF₃ CH₂ CH₃ O A2  CF₃ CH₂ CH₂CH₃ O A3  CF₃ CH₂ (CH₃)₂CH O A4  CF₃ CH₂ PhCH₂ O A5  CF₃ CH₂ CH₃ S A6  CF₃ CH₂ CH₃ SO A7  CF₃ CH₂ CH₃ SO₂ A8  CF₃ CH₂ CH₃OCH₂ O A9  CF₃ CH₂ CH₃CH₂OCH₂ O A10  CF₃ CH₂ CH₃OCH₂CH₂ O A11  CF₃ CH₂ CH₃CH₂OCH₂CH₂ O A12  CF₃ CH₂ CH₃OC(CH₃)₂CH₂ O A13  CF₃ CH₂ CH₃OCH(CH₃)CH₂ O A14  CF₃ CH₂ CH₃OCH₂CH(CH₃) O A15  CF₃ CH₂ CH₃OCH₂C(CH₃)₂ O A16  CF₃ CH₂ CH₃OCH(CH₃) O A17  CF₃ CH₂ CH₃OC(CH₃)₂ O A18  CF₃ CH₂ HC≡CCH₂ O A19  CF₃ CH₂ H₂C═CHCH₂ O A20  CF₃ CH₂ CH₃C≡CCH₂ O A21  CF₃ CH₂

O A22  CF₃ CH₂CH₂CH₂

O A23  CF₃ CH₂

O A24  CF₃ CH₂

O A25  CF₃ CH₂

O A26  CF₃ CH₂

O A27  CF₃ CH₂

O A28  CF₃ CH₂

O A29  CF₃ CH₂

O A30  CF₃ CH₂

O A31  CF₃ CH₂

O A32  CF₃ CH₂

O A33  CF₃ CH₂

O A34  CF₃ CH₂

O A35  CF₃ CH₂

O A36  CF₃ CH₂

O A37  CF₃ CH₂

O A38  CF₃ CH₂

O A39  CF₃ CH₂

O A40  CF₃ CH₂

O A41  CF₃ CH₂

O A42  CF₃ CH₂

O A43  CF₃ CH₂

O A44  CF₃ CH₂

O A45  CF₃ CH₂

O A46  CF₃ CH₂

O A47  CF₃ CH₂

O A48  CF₃ CH₂

O A49  CF₃ CH₂

O A50  CF₃ CH₂

O A51  CF₃ CH₂

O A52  CF₃ CH₂

O A53  CF₃ CH₂

O A54  CF₃ CH₂

O A55  CF₃ CH₂

O A56  CF₃ CH₂

O A57  CF₃ CH₂

O A58  CF₃ CH₂

O A59  CF₃ CH₂

O A60  CF₃ CH₂

O A61  CF₃ CH₂

O A62  CF₃ CH₂

O A63  CF₃ CH₂

O A64  CF₃ CH₂

O A65  CF₃ CH₂

O A66  CF₃ CH₂

O A67  CF₃ CH₂

O A68  CF₃ CH₂

O A69  CF₃ CH₂

O A70  CF₃ CH₂

O A71  CF₃ CH₂

O A72  CF₃ CH₂

O A73  CF₃ CH₂

O A74  CF₃ CH₂

O A75  CF₃ CH₂

O A76  CF₃ CH₂

O A77  CF₃ CH₂

O A78  CF₃ CH₂

O A79  CF₃ CH₂

O A80  CF₃ CH₂

O A81  CF₃ CH₂

O A82  CF₃ CH₂

O A83  CF₃ CH₂

O A84  CF₃ CH₂

O A85  CF₃ CH₂

O A86  CF₃ CH₂

O A87  CF₃ CH₂

O A88  CF₃ CH₂

O A89  CF₃ CH₂

O A90  CF₃ CH₂

O A91  CF₃ CH₂CH₂ CH₃ O A92  CF₃ CH₂CH₂ CH₃CH₂ O A93  CF₃ CH₂CH₂ (CH₃)₂CH O A94  CF₃ CH₂CH₂ PhCH₂ O A95  CF₃ CH₂CH₂ CH₃ S A96  CF₃ CH₂CH₂ CH₃ SO A97  CF₃ CH₂CH₂ CH₃ SO₂ A98  CF₃ CH₂CH₂ (CH₃)₂CHCH₂ O A99  CF₃ CH₂CH₂ CH₃OCH₂ O A100 CF₃ CH₂CH₂ CH₃CH₂OCH₂ O A101 CF₃ CH₂CH₂ CH₃OCH₂CH₂ O A102 CF₃ CH₂CH₂ CH₃CH₂OCH₂CH₂ O A103 CF₃ CH₂CH₂ CH₃OC(CH₃)₂CH₂ O A104 CF₃ CH₂CH₂ CH₃OCH(CH₃)CH₂ O A105 CF₃ CH₂CH₂ CH₃OCH₂CH(CH₃) O A106 CF₃ CH₂CH₂ CH₃OCH₂C(CH₃)₂ O A107 CF₃ CH₂CH₂ CH₃OCH(CH₃) O A108 CF₃ CH₂CH₂ CH₃OC(CH₃)₂ O A109 CF₃ CH₂CH₂ HC≡CCH₂ O A110 CF₃ CH₂CH₂ H₂C═CHCH₂ O A111 CF₃ CH₂CH₂ CH₃C≡CCH₂ O A112 CF₃ CH₂CH₂

O A113 CF₃ CH₂CH₂CH₂

O A114 CF₃ CH₂CH₂

O A115 CF₃ CH₂CH₂

O A116 CF₃ CH₂CH₂

O A117 CF₃ CH₂CH₂

O A118 CF₃ CH₂CH₂

O A119 CF₃ CH₂CH₂

O A120 CF₃ CH₂CH₂

O A121 CF₃ CH₂CH₂

O A122 CF₃ CH₂CH₂

O A123 CF₃ CH₂CH₂

O A124 CF₃ CH₂CH₂

O A125 CF₃ CH₂CH₂

O A126 CF₃ CH₂CH₂

O A127 CF₃ CH₂CH₂

O A128 CF₃ CH₂CH₂

O A129 CF₃ CH₂CH₂

O A130 CF₃ CH₂CH₂

O A131 CF₃ CH₂CH₂

O A132 CF₃ CH₂CH₂

O A133 CF₃ CH₂CH₂

O A134 CF₃ CH₂CH₂

O A135 CF₃ CH₂CH₂

O A136 CF₃ CH₂CH₂

O A137 CF₃ CH₂CH₂

O A138 CF₃ CH₂CH₂

O A139 CF₃ CH₂CH₂

O A140 CF₃ CH₂CH₂

O A141 CF₃ CH₂CH₂

O A142 CF₃ CH₂CH₂

O A143 CF₃ CH₂CH₂

O A144 CF₃ CH₂CH₂

O A145 CF₃ CH₂CH₂

O A146 CF₃ CH₂CH₂

O A147 CF₃ CH₂CH₂

O A148 CF₃ CH₂CH₂

O A149 CF₃ CH₂CH₂

O A150 CF₃ CH₂CH₂

O A151 CF₃ CH₂CH₂

O A152 CF₃ CH₂CH₂

O A153 CF₃ CH₂CH₂

O A154 CF₃ CH₂CH₂

O A155 CF₃ CH₂CH₂

O A156 CF₃ CH₂CH₂

O A157 CF₃ CH₂CH₂

O A158 CF₃ CH₂CH₂

O A159 CF₃ CH₂CH₂

O A160 CF₃ CH₂CH₂

O A161 CF₃ CH₂CH₂

O A162 CF₃ CH₂CH₂

O A163 CF₃ CH₂CH₂

O A164 CF₃ CH₂CH₂

O A165 CF₃ CH₂CH₂

O A166 CF₃ CH₂CH₂

O A167 CF₃ CH₂CH₂

O A168 CF₃ CH₂CH₂

O A169 CF₃ CH₂CH₂

O A170 CF₃ CH₂CH₂

O A171 CF₃ CH₂CH₂

O A172 CF₃ CH₂CH₂

O A173 CF₃ CH₂CH₂

O A174 CF₃ CH₂CH₂

O A175 CF₃ CH₂CH₂

O A176 CF₃ CH₂CH₂

O A177 CF₃ CH₂CH₂

O A178 CF₃ CH₂CH₂

O A179 CF₃ CH₂CH₂

O A180 CF₃ CH₂CH₂

O A181 CF₃ CH₂CH₂

O A182 CF₃ CH(OCH₃)CH₂ CH₃ O A183 CF₃ CH(OCH₃)CH₂ CH₃CH₂ O A184 CF₃ CH(OCH₃)CH₂ (CH₃)₂CH O A185 CF₃ CH(OCH₃)CH₂ PhCH₂ O A186 CF₃ CH(OCH₃)CH₂ CH₃ S A187 CF₃ CH(OCH₃)CH₂ CH₃ SO A188 CF₃ CH(OCH₃)CH₂ CH₃ SO₂ A189 CF₃ CH(OCH₃)CH₂ CH₃CH₂CH₂ O A190 CF₃ CH(OCH₃)CH₂ CH₃OCH₂ O A191 CF₃ CH(OCH₃)CH₂ CH₃CH₂OCH₂ O A192 CF₃ CH(OCH₃)CH₂ CH₃OCH₂CH₂ O A193 CF₃ CH(OCH₃)CH₂ CH₃CH₂OCH₂CH₂ O A194 CF₃ CH(OCH₃)CH₂ CH₃OC(CH₃)₂CH₂ O A195 CF₃ CH(OCH₃)CH₂ CH₃OCH(CH₃)CH₂ O A196 CF₃ CH(0CH₃)CH₂ CH₃OCH₂CH(CH₃) O A197 CF₃ CH(OCH₃)CH₂ CH₃OCH₂C(CH₃)₂ O A198 CF₃ CH(OCH₃)CH₂ CH₃OCH(CH₃) O A199 CF₃ CH(OCH₃)CH₂ CH₃OC(CH₃)₂ O A200 CF₃ CH(OCH₃)CH₂ HC≡CCH₂ O A201 CF₃ CH(OCH₃)CH₂ H₂C═CHCH₂ O A202 CF₃ CH(OCH₃)CH₂ CH₃C≡CCH₂ O A203 CF₃ CH(OCH₃)CH₂

O A204 CF₃ CH₂CH₂CH₂

O A205 CF₃ CH(OCH₃)CH₂

O A206 CF₃ CH(OCH₃)CH₂

O A207 CF₃ CH(OCH₃)CH₂

O A208 CF₃ CH(OCH₃)CH₂

O A209 CF₃ CH(OCH₃)CH₂

O A210 CF₃ CH(OCH₃)CH₂

O A211 CF₃ CH(OCH₃)CH₂

O A212 CF₃ CH(OCH₃)CH₂

O A213 CF₃ CH(OCH₃)CH₂

O A214 CF₃ CH(OCH₃)CH₂

O A215 CF₃ CH(OCH₃)CH₂

O A216 CF₃ CH(OCH₃)CH₂

O A217 CF₃ CH(OCH₃)CH₂

O A218 CF₃ CH(OCH₃)CH₂

O A219 CF₃ CH(OCH₃)CH₂

O A220 CF₃ CH(OCH₃)CH₂

O A221 CF₃ CH(OCH₃)CH₂

O A222 CF₃ CH(OCH₃)CH₂

O A223 CF₃ CH(OCH₃)CH₂

O A224 CF₃ CH(OCH₃)CH₂

O A225 CF₃ CH(OCH₃)CH₂

O A226 CF₃ CH(OCH₃)CH₂

O A227 CF₃ CH(OCH₃)CH₂

O A228 CF₃ CH(OCH₃)CH₂

O A229 CF₃ CH(OCH₃)CH₂

O A230 CF₃ CH(OCH₃)CH₂

O A231 CF₃ CH(OCH₃)CH₂

O A232 CF₃ CH(OCH₃)CH₂

O A233 CF₃ CH(OCH₃)CH₂

O A234 CF₃ CH(OCH₃)CH₂

O A235 CF₃ CH(OCH₃)CH₂

O A236 CF₃ CH(OCH₃)CH₂

O A237 CF₃ CH(OCH₃)CH₂

O A238 CF₃ CH(OCH₃)CH₂

O A239 CF₃ CH(OCH₃)CH₂

O A240 CF₃ CH(OCH₃)CH₂

O A241 CF₃ CH(OCH₃)CH₂

O A242 CF₃ CH(OCH₃)CH₂

O A243 CF₃ CH(OCH₃)CH₂

O A244 CF₃ CH(OCH₃)CH₂

O A245 CF₃ CH(OCH₃)CH₂

O A246 CF₃ CH(OCH₃)CH₂

O A247 CF₃ CH(OCH₃)CH₂

O A248 CF₃ CH(OCH₃)CH₂

O A249 CF₃ CH(OCH₃)CH₂

O A250 CF₃ CH(OCH₃)CH₂

O A251 CF₃ CH(OCH₃)CH₂

O A252 CF₃ CH(OCH₃)CH₂

O A253 CF₃ CH(OCH₃)CH₂

O A254 CF₃ CH(OCH₃)CH₂

O A255 CF₃ CH(OCH₃)CH₂

O A256 CF₃ CH(OCH₃)CH₂

O A257 CF₃ CH(OCH₃)CH₂

O A258 CF₃ CH(OCH₃)CH₂

O A259 CF₃ CH(OCH₃)CH₂

O A260 CF₃ CH(OCH₃)CH₂

O A261 CF₃ CH(OCH₃)CH₂

O A262 CF₃ CH(OCH₃)CH₂

O A263 CF₃ CH(OCH₃)CH₂

O A264 CF₃ CH(OCH₃)CH₂

O A265 CF₃ CH(OCH₃)CH₂

O A266 CF₃ CH(OCH₃)CH₂

O A267 CF₃ CH(OCH₃)CH₂

O A268 CF₃ CH(OCH₃)CH₂

O A269 CF₃ CH(OCH₃)CH₂

O A270 CF₃ CH(OCH₃)CH₂

O A271 CF₃ CH(OCH₃)CH₂

O A272 CF₃ CH(OCH₃)CH₂

O A273 CF₃ CH₂CH(OCH₃)CH₂ CH₃ O A274 CF₃ CH₂CH(OCH₃)CH₂ CH₃CH₂ O A275 CF₃ CH₂CH(OCH₃)CH₂ (CH₃)₂CH O A276 CF₃ CH₂CH(OCH₃)CH₂ PhCH₂ O A277 CF₃ CH₂CH(OCH₃)CH₂ CH₃ S A278 CF₃ CH₂CH(OCH₃)CH₂ CH₃ SO A279 CF₃ CH₂CH(OCH₃)CH₂ CH₃ SO₂ A280 CF₃ CH₂CH(OCH₃)CH₂ CH₃CH₂CH₂ O A281 CF₃ CH₂CH(OCH₃)CH₂ CH₃OCH₂ O A282 CF₃ CH₂CH(OCH₃)CH₂ CH₃CH₂OCH₂ O A283 CF₃ CH₂CH(OCH₃)CH₂ CH₃OCH₂CH₂ O A284 CF₃ CH₂CH(OCH₃)CH₂ CH₃CH₂OCH₂CH₂ O A285 CF₃ CH₂CH(OCH₃)CH₂ CH₃OC(CH₃)₂CH₂ O A286 CF₃ CH₂CH(OCH₃)CH₂ CH₃OCH(CH₃)CH₂ O A287 CF₃ CH₂CH(OCH₃)CH₂ CH₃OCH₂CH(CH₃) O A288 CF₃ CH₂CH(OCH₃)CH₂ CH₃OCH₂C(CH₃)₂ O A289 CF₃ CH₂CH(OCH₃)CH₂ CH₃OCH(CH₃) O A290 CF₃ CH₂CH(OCH₃)CH₂ CH₃OC(CH₃)₂ O A291 CF₃ CH₂CH(OCH₃)CH₂ HC≡CCH₂ O A292 CF₃ CH₂CH(OCH₃)CH₂ H₂C═CHCH₂ O A293 CF₃ CH₂CH(OCH₃)CH₂ CH₃C≡CCH₂ O A294 CF₃ CH₂CH(OCH₃)CH₂

O A295 CF₃ CH₂CH₂CH₂

O A296 CF₃ CH₂CH(OCH₃)CH₂

O A297 CF₃ CH₂CH(OCH₃)CH₂

O A298 CF₃ CH₂CH(OCH₃)CH₂

O A299 CF₃ CH₂CH(OCH₃)CH₂

O A300 CF₃ CH₂CH(OCH₃)CH₂

O A301 CF₃ CH₂CH(OCH₃)CH₂

O A302 CF₃ CH₂CH(OCH₃)CH₂

O A303 CF₃ CH₂CH(OCH₃)CH₂

O A304 CF₃ CH₂CH(OCH₃)CH₂

O A305 CF₃ CH₂CH(OCH₃)CH₂

O A306 CF₃ CH₂CH(OCH₃)CH₂

O A307 CF₃ CH₂CH(OCH₃)CH₂

O A308 CF₃ CH₂CH(OCH₃)CH₂

O A309 CF₃ CH₂CH(OCH₃)CH₂

O A310 CF₃ CH₂CH(OCH₃)CH₂

O A311 CF₃ CH₂CH(OCH₃)CH₂

O A312 CF₃ CH₂CH(OCH₃)CH₂

O A313 CF₃ CH₂CH(OCH₃)CH₂

O A314 CF₃ CH₂CH(OCH₃)CH₂

O A315 CF₃ CH₂CH(OCH₃)CH₂

O A316 CF₃ CH₂CH(OCH₃)CH₂

O A317 CF₃ CH₂CH(OCH₃)CH₂

O A318 CF₃ CH₂CH(OCH₃)CH₂

O A319 CF₃ CH₂CH(OCH₃)CH₂

O A320 CF₃ CH₂CH(OCH₃)CH₂

O A321 CF₃ CH₂CH(OCH₃)CH₂

O A322 CF₃ CH₂CH(OCH₃)CH₂

O A323 CF₃ CH₂CH(OCH₃)CH₂

O A324 CF₃ CH₂CH(OCH₃)CH₂

O A325 CF₃ CH₂CH(OCH₃)CH₂

O A326 CF₃ CH₂CH(OCH₃)CH₂

O A327 CF₃ CH₂CH(OCH₃)CH₂

O A328 CF₃ CH₂CH(OCH₃)CH₂

O A329 CF₃ CH₂CH(OCH₃)CH₂

O A330 CF₃ CH₂CH(OCH₃)CH₂

O A331 CF₃ CH₂CH(OCH₃)CH₂

O A332 CF₃ CH₂CH(OCH₃)CH₂

O A333 CF₃ CH₂CH(OCH₃)CH₂

O A334 CF₃ CH₂CH(OCH₃)CH₂

O A335 CF₃ CH₂CH(OCH₃)CH₂

O A336 CF₃ CH₂CH(OCH₃)CH₂

O A337 CF₃ CH₂CH(OCH₃)CH₂

O A338 CF₃ CH₂CH(OCH₃)CH₂

O A339 CF₃ CH₂CH(OCH₃)CH₂

O A340 CF₃ CH₂CH(OCH₃)CH₂

O A341 CF₃ CH₂CH(OCH₃)CH₂

O A342 CF₃ CH₂CH(OCH₃)CH₂

O A343 CF₃ CH₂CH(OCH₃)CH₂

O A344 CF₃ CH₂CH(OCH₃)CH₂

O A345 CF₃ CH₂CH(OCH₃)CH₂

O A346 CF₃ CH₂CH(OCH₃)CH₂

O A347 CF₃ CH₂CH(OCH₃)CH₂

O A348 CF₃ CH₂CH(OCH₃)CH₂

O A349 CF₃ CH₂CH(OCH₃)CH₂

O A350 CF₃ CH₂CH(OCH₃)CH₂

O A351 CF₃ CH₂CH(OCH₃)CH₂

O A352 CF₃ CH₂CH(OCH₃)CH₂

O A353 CF₃ CH₂CH(OCH₃)CH₂

O A354 CF₃ CH₂CH(OCH₃)CH₂

O A355 CF₃ CH₂CH(OCH₃)CH₂

O A356 CF₃ CH₂CH(OCH₃)CH₂

O A357 CF₃ CH₂CH(OCH₃)CH₂

O A358 CF₃ CH₂CH(OCH₃)CH₂

O A359 CF₃ CH₂CH(OCH₃)CH₂

O A360 CF₃ CH₂CH(OCH₃)CH₂

O A361 CF₃ CH₂CH(OCH₃)CH₂

O A362 CF₃ CH₂CH(OCH₃)CH₂

O A363 CF₃ CH₂CH(OCH₃)CH₂

O A364 CF₃ CH═CHCH₂ CH₃ O A365 CF₃ CH═CHCH₂ CH₃CH₂ O A366 CF₃ CH═CHCH₂ (CH₃)₂CH O A367 CF₃ CH═CHCH₂ PhCH₂ O A368 CF₃ CH═CHCH₂ CH₃ S A369 CF₃ CH═CHCH₂ CH₃ SO A370 CF₃ CH═CHCH₂ CH₃ SO₂ A371 CF₃ CH═CHCH₂ CH₃CH₂CH₂ O A372 CF₃ CH═CHCH₂ CH₃OCH₂ O A373 CF₃ CH═CHCH₂ CH₃CH₂OCH₂ O A374 CF₃ CH═CHCH₂ CH₃OCH₂CH₂ O A375 CF₃ CH═CHCH₂ CH₃CH₂OCH₂CH₂ O A376 CF₃ CH═CHCH₂ CH₃OC(CH₃)₂CH₂ O A377 CF₃ CH═CHCH₂ CH₃OCH(CH₃)CH₂ O A378 CF₃ CH═CHCH₂ CH₃OCH₂CH(CH₃) O A379 CF₃ CH═CHCH₂ CH₃OCH₂C(CH₃)₂ O A380 CF₃ CH═CHCH₂ CH₃OCH(CH₃) O A381 CF₃ CH═CHCH₂ CH₃OC(CH₃)₂ O A382 CF₃ CH═CHCH₂ HC≡CCH₂ O A383 CF₃ CH═CHCH₂ H₂C═CHCH₂ O A384 CF₃ CH═CHCH₂ CH₃C≡CCH₂ O A385 CF₃ CH═CHCH₂

O A386 CF₃ CH═CHCH₂

O A387 CF₃ CH═CHCH₂

O A388 CF₃ CH═CHCH₂

O A389 CF₃ CH═CHCH₂

O A390 CF₃ CH═CHCH₂

O A391 CF₃ CH═CHCH₂

O A392 CF₃ CH═CHCH₂

O A393 CF₃ CH═CHCH₂

O A394 CF₃ CH═CHCH₂

O A395 CF₃ CH═CHCH₂

O A396 CF₃ CH═CHCH₂

O A397 CF₃ CH═CHCH₂

O A398 CF₃ CH═CHCH₂

O A399 CF₃ CH═CHCH₂

O A400 CF₃ CH═CHCH₂

O A401 CF₃ CH═CHCH₂

O A402 CF₃ CH═CHCH₂

O A403 CF₃ CH═CHCH₂

O A404 CF₃ CH═CHCH₂

O A405 CF₃ CH═CHCH₂

O A406 CF₃ CH═CHCH₂

O A407 CF₃ CH═CHCH₂

O A408 CF₃ CH═CHCH₂

O A409 CF₃ CH═CHCH₂

O A410 CF₃ CH═CHCH₂

O A411 CF₃ CH═CHCH₂

O A412 CF₃ CH═CHCH₂

O A413 CF₃ CH═CHCH₂

O A414 CF₃ CH═CHCH₂

O A415 CF₃ CH═CHCH₂

O A416 CF₃ CH═CHCH₂

O A417 CF₃ CH═CHCH₂

O A418 CF₃ CH═CHCH₂

O A419 CF₃ CH═CHCH₂

O A420 CF₃ CH═CHCH₂

O A421 CF₃ CH═CHCH₂

O A422 CF₃ CH═CHCH₂

O A423 CF₃ CH═CHCH₂

O A424 CF₃ CH═CHCH₂

O A425 CF₃ CH═CHCH₂

O A426 CF₃ CH═CHCH₂

O A427 CF₃ CH═CHCH₂

O A428 CF₃ CH═CHCH₂

O A429 CF₃ CH═CHCH₂

O A430 CF₃ CH═CHCH₂

O A431 CF₃ CH═CHCH₂

O A432 CF₃ CH═CHCH₂

O A433 CF₃ CH═CHCH₂

O A434 CF₃ CH═CHCH₂

O A435 CF₃ CH═CHCH₂

O A436 CF₃ CH═CHCH₂

O A437 CF₃ CH═CHCH₂

O A438 CF₃ CH═CHCH₂

O A439 CF₃ CH═CHCH₂

O A440 CF₃ CH═CHCH₂

O A441 CF₃ CH═CHCH₂

O A442 CF₃ CH═CHCH₂

O A443 CF₃ CH═CHCH₂

O A444 CF₃ CH═CHCH₂

O A445 CF₃ CH═CHCH₂

O A446 CF₃ CH═CHCH₂

O A447 CF₃ CH═CHCH₂

O A448 CF₃ CH═CHCH₂

O A449 CF₃ CH═CHCH₂

O A450 CF₃ CH═CHCH₂

O A451 CF₃ CH═CHCH₂

O A452 CF₃ CH═CHCH₂

O A453 CF₃ CH═CHCH₂

O A454 CF₃ CH═CHCH₂

O A455 CF₃ C≡CCH₂ CH₃ O A456 CF₃ C≡CCH₂ CH₃CH₂ O A457 CF₃ C≡CCH₂ (CH₃)₂CH O A458 CF₃ C≡CCH₂ PhCH₂ O A459 CF₃ C≡CCH₂ CH₃ S A460 CF₃ C≡CCH₂ CH₃ SO A461 CF₃ C≡CCH₂ CH₃ SO₂ A462 CF₃ C≡CCH₂ CH₃CH₂CH₂ O A463 CF₃ C≡CCH₂ CH₃OCH₂ O A464 CF₃ C≡CCH₂ CH₃CH₂OCH₂ O A465 CF₃ C≡CCH₂ CH₃OCH₂CH₂ O A466 CF₃ C≡CCH₂ CH₃CH₂OCH₂CH₂ O A467 CF₃ C≡CCH₂ CH₃OC(CH₃)₂CH₂ O A468 CF₃ C≡CCH₂ CH₃OCH(CH₃)CH₂ O A469 CF₃ C≡CCH₂ CH₃OCH₂CH(CH₃) O A470 CF₃ C≡CCH₂ CH₃OCH₂C(CH₃)₂ O A471 CF₃ C≡CCH₂ CH₃OCH(CH₃) O A472 CF₃ C≡CCH₂ CH₃OC(CH₃)₂ O A473 CF₃ C≡CCH₂ HC≡CCH₂ O A474 CF₃ C≡CCH₂ H₂C═CHCH₂ O A475 CF₃ C≡CCH₂ CH₃C≡CCH₂ O A476 CF₃ C≡CCH₂

O A477 CF₃ C≡CCH₂

O A478 CF₃ C≡CCH₂

O A479 CF₃ C≡CCH₂

O A480 CF₃ C≡CCH₂

O A481 CF₃ C≡CCH₂

O A482 CF₃ C≡CCH₂

O A483 CF₃ C≡CCH₂

O A484 CF₃ C≡CCH₂

O A485 CF₃ C≡CCH₂

O A486 CF₃ C≡CCH₂

O A487 CF₃ C≡CCH₂

O A488 CF₃ C≡CCH₂

O A489 CF₃ C≡CCH₂

O A490 CF₃ C≡CCH₂

O A491 CF₃ C≡CCH₂

O A492 CF₃ C≡CCH₂

O A493 CF₃ C≡CCH₂

O A494 CF₃ C≡CCH₂

O A495 CF₃ C≡CCH₂

O A496 CF₃ C≡CCH₂

O A497 CF₃ C≡CCH₂

O A498 CF₃ C≡CCH₂

O A499 CF₃ C≡CCH₂

O A500 CF₃ C≡CCH₂

O A501 CF₃ C≡CCH₂

O A502 CF₃ C≡CCH₂

O A503 CF₃ C≡CCH₂

O A504 CF₃ C≡CCH₂

O A505 CF₃ C≡CCH₂

O A506 CF₃ C≡CCH₂

O A507 CF₃ C≡CCH₂

O A508 CF₃ C≡CCH₂

O A509 CF₃ C≡CCH₂

O A510 CF₃ C≡CCH₂

O A511 CF₃ C≡CCH₂

O A512 CF₃ C≡CCH₂

O A513 CF₃ C≡CCH₂

O A514 CF₃ C≡CCH₂

O A515 CF₃ C≡CCH₂

O A516 CF₃ C≡CCH₂

O A517 CF₃ C≡CCH₂

O A518 CF₃ C≡CCH₂

O A519 CF₃ C≡CCH₂

O A520 CF₃ C≡CCH₂

O A521 CF₃ C≡CCH₂

O A521a CF₃ C≡CCH₂

O A522 CF₃ C≡CCH₂

O A523 CF₃ C≡CCH₂

O A524 CF₃ C≡CCH₂

O A525 CF₃ C≡CCH₂

O A526 CF₃ C≡CCH₂

O A527 CF₃ C≡CCH₂

O A528 CF₃ C≡CCH₂

O A529 CF₃ C≡CCH₂

O A530 CF₃ C≡CCH₂

O A531 CF₃ C≡CCH₂

O A532 CF₃ C≡CCH₂

O

Comp. no. R₄ R₁ R₂ X₁ A533 CF₃ C≡CCH₂

O A534 CF₃ C≡CCH₂

O A535 CF₃ C≡CCH₂

O A536 CF₃ C≡CCH₂

O A537 CF₃ C≡CCH₂

O A538 CF₃ C≡CCH₂

O A539 CF₃ C≡CCH₂

O A540 CF₃ C≡CCH₂

O A541 CF₃ C≡CCH₂

O A542 CF₃ C≡CCH₂

O A543 CF₃ C≡CCH₂

O A544 CF₃ C≡CCH₂

O A545 CF₃ C≡CCH₂

O A546 CF₂Cl CH₂ CH₃ O A547 CF₂Cl CH₂ CH₃CH₂ O A548 CF₂Cl CH₂ (CH₃)₂CH O A549 CF₂Cl CH₂ PhCH₂ O A550 CF₂Cl CH₂ CH₃ S A551 CF₂Cl CH₂ CH₃ SO A552 CF₂Cl CH₂ CH₃ SO₂ A553 CF₂Cl CH₂ CH₃CH₂CH₂ O A554 CF₂Cl CH₂ CH₃OCH₂ O A555 CF₂Cl CH₂ CH₃CH₂OCH₂ O A556 CF₂Cl CH₂ CH₃OCH₂CH₂ O A557 CF₂Cl CH₂ CH₃CH₂OCH₂CH₂ O A558 CF₂Cl CH₂ CH₃OC(CH₃)₂CH₂ O A559 CF₂Cl CH₂ CH₃OCH(CH₃)CH₂ O A560 CF₂Cl CH₂ CH₃OCH₂CH(CH₃) O A561 CF₂Cl CH₂ CH₃OCH₂C(CH₃)₂ O A562 CF₂Cl CH₂ CH₃OCH(CH₃) O A563 CF₂Cl CH₂ CH₃OC(CH₃)₂ O A564 CF₂Cl CH₂ HC≡CCH₂ O A565 CF₂Cl CH₂ H₂C═CHCH₂ O A566 CF₂Cl CH₂ CH₃C≡CCH₂ O A567 CF₂Cl CH₂

O A568 CF₂Cl CH₂

O A569 CF₂Cl CH₂

O A570 CF₂Cl CH₂

O A571 CF₂Cl CH₂

O A572 CF₂Cl CH₂

O A573 CF₂Cl CH₂

O A574 CF₂Cl CH₂

O A575 CF₂Cl CH₂

O A576 CF₂Cl CH₂

O A577 CF₂Cl CH₂

O A578 CF₂Cl CH₂

O A579 CF₂Cl CH₂

O A580 CF₂Cl CH₂

O A581 CF₂Cl CH₂

O A582 CF₂Cl CH₂

O A583 CF₂Cl CH₂

O A584 CF₂Cl CH₂

O A585 CF₂Cl CH₂

O A586 CF₂Cl CH₂

O A587 CF₂Cl CH₂

O A588 CF₂Cl CH₂

O A589 CF₂Cl CH₂

O A590 CF₂Cl CH₂

O A591 CF₂Cl CH₂

O A592 CF₂Cl CH₂

O A593 CF₂Cl CH₂

O A594 CF₂Cl CH₂

O A595 CF₂Cl CH₂

O A596 CF₂Cl CH₂

O A597 CF₂Cl CH₂

O A598 CF₂Cl CH₂

O A599 CF₂Cl CH₂

O A600 CF₂Cl CH₂

O A601 CF₂Cl CH₂

O A602 CF₂Cl CH₂

O A603 CF₂Cl CH₂

O A604 CF₂Cl CH₂

O A605 CF₂Cl CH₂

O A606 CF₂Cl CH₂

O A607 CF₂Cl CH₂

O A608 CF₂Cl CH₂

O A609 CF₂Cl CH₂

O A610 CF₂Cl CH₂

O A611 CF₂Cl CH₂

O A612 CF₂Cl CH₂

O A613 CF₂Cl CH₂

O A614 CF₂Cl CH₂

O A615 CF₂Cl CH₂

O A616 CF₂Cl CH₂

O A617 CF₂Cl CH₂

O A618 CF₂Cl CH₂

O A619 CF₂Cl CH₂

O A620 CF₂Cl CH₂

O A621 CF₂Cl CH₂

O A622 CF₂Cl CH₂

O A623 CF₂Cl CH₂

O A624 CF₂Cl CH₂

O A625 CF₂Cl CH₂

O A626 CF₂Cl CH₂

O A627 CF₂Cl CH₂

O A628 CF₂Cl CH₂

O A629 CF₂Cl CH₂

O A630 CF₂Cl CH₂

O A631 CF₂Cl CH₂

O A632 CF₂Cl CH₂

O A633 CF₂Cl CH₂

O A634 CF₂Cl CH₂

O A635 CF₂Cl CH₂

O A636 CF₂Cl CH₂

O A637 CF₂Cl CH₂ CH₃ O A638 CF₂Cl CH₂ CH₂CH₃ O A639 CF₂Cl CH₂ (CH₃)₂CH O A640 CF₂Cl CH₂ PhCH₂ O A641 CF₂Cl CH₂ CH₃ S A642 CF₂Cl CH₂ CH₃ O A643 CF₂Cl CH₂ CH₃ O A644 CF₂Cl CH₂ CH₃OCH₂ O A645 CF₂Cl CH₂ CH₃CH₂OCH₂ O A646 CF₂Cl CH₂ CH₃OCH₂CH₂ O A647 CF₂Cl CH₂ CH₃CH₂OCH₂CH₂ O A648 CF₂Cl CH₂ CH₃OC(CH₃)₂CH₂ O A649 CF₂Cl CH₂ CH₃OCH(CH₃)CH₂ O A650 CF₂Cl CH₂ CH₃OCH₂CH(CH₃) O A651 CF₂Cl CH₂ CH₃OCH₂C(CH₃)₂ O A652 CF₂Cl CH₂ CH₃OCH(CH₃) O A653 CF₂Cl CH₂ CH₃OC(CH₃)₂ O A654 CF₂Cl CH₂ HC≡CCH₂ O A655 CF₂Cl CH₂ H₂C═CHCH₂ O A656 CF₂Cl CH₂ CH₃C≡CCH₂ O A657 CF₂Cl CH₂

O A658 CF₂Cl CH₂

O A659 CF₂Cl CH₂

O A660 CF₂Cl CH₂

O A661 CF₂Cl CH₂

O A662 CF₂Cl CH₂

O A663 CF₂Cl CH₂

O A664 CF₂Cl CH₂

O A665 CF₂Cl CH₂

O A666 CF₂Cl CH₂

O A667 CF₂Cl CH₂

O A668 CF₂Cl CH₂

O A669 CF₂Cl CH₂

O A670 CF₂Cl CH₂

O A671 CF₂Cl CH₂

O A672 CF₂Cl CH₂

O A673 CF₂Cl CH₂

O A674 CF₂Cl CH₂

O A675 CF₂Cl CH₂

O A676 CF₂Cl CH₂

O A677 CF₂Cl CH₂

O A678 CF₂Cl CH₂

O A679 CF₂Cl CH₂

O A680 CF₂Cl CH₂

O A681 CF₂Cl CH₂

O A682 CF₂Cl CH₂

S A683 CF₂Cl CH₂

SO A684 CF₂Cl CH₂

SO₂ A685 CF₂Cl CH₂

O A686 CF₂Cl CH₂

O A687 CF₂Cl CH₂

O A688 CF₂Cl CH₂

O A689 CF₂Cl CH₂

O A690 CF₂Cl CH₂

O A691 CF₂Cl CH₂

O A692 CF₂Cl CH₂

O A693 CF₂Cl CH₂

O A694 CF₂Cl CH₂

O A695 CF₂Cl CH₂

O A696 CF₂Cl CH₂

O A697 CF₂Cl CH₂

O A698 CF₂Cl CH₂

O A699 CF₂Cl CH₂

O A700 CF₂Cl CH₂

O A701 CF₂Cl CH₂

O A702 CF₂Cl CH₂

O A703 CF₂Cl CH₂

O A704 CF₂Cl CH₂

O A705 CF₂Cl CH₂

O A706 CF₂Cl CH₂

O A707 CF₂Cl CH₂

O A708 CF₂Cl CH₂

O A709 CF₂Cl CH₂

O A710 CF₂Cl CH₂

O A711 CF₂Cl CH₂

O A712 CF₂Cl CH₂

O A713 CF₂Cl CH₂

O A714 CF₂Cl CH₂

O A715 CF₂Cl CH₂

O A716 CF₂Cl CH₂

O A717 CF₂Cl CH₂

O A718 CF₂Cl CH₂

O A719 CF₂Cl CH₂

O A720 CF₂Cl CH₂

O A721 CF₂Cl CH₂

O A722 CF₂Cl CH₂

O A723 CF₂Cl CH₂

O A724 CF₂Cl CH₂

O A725 CF₂Cl CH₂

O A726 CF₂Cl CH₂

O A727 CF₂Cl CH₂ CH₃ O A728 CF₂Cl CH₂ CH₂CH₃ O A729 CF₂Cl CH₂ (CH₃)₂CH O A730 CF₂Cl CH₂ PhCH₂ O A731 CF₂Cl CH₂ CH₃ S A732 CF₂Cl CH₂ CH₃ SO A733 CF₂Cl CH₂ CH₃ SO₂ A734 CF₂Cl CH₂ CH₃OCH₂ O A735 CF₂Cl CH₂ CH₃CH₂OCH₂ O A736 CF₂Cl CH₂ CH₃OCH₂CH₂ O A737 CF₂Cl CH₂ CH₃CH₂OCH₂CH₂ O A738 CF₂Cl CH₂ CH₃OC(CH₃)₂CH₂ O A739 CF₂Cl CH₂ CH₃OCH(CH₃)CH₂ O A740 CF₂Cl CH₂ CH₃OCH₂CH(CH₃) O A741 CF₂Cl CH₂ CH₃OCH₂C(CH₃)₂ O A742 CF₂Cl CH₂ CH₃OCH(CH₃) O A743 CF₂Cl CH₂ CH₃OC(CH₃)₂ O A744 CF₂Cl CH₂ HC≡CCH₂ O A745 CF₂Cl CH₂ H₂C═CHCH₂ O A746 CF₂Cl CH₂ CH₃C≡CCH₂ O A747 CF₂Cl CH₂

O A748 CF₂Cl CH₂

O A749 CF₂Cl CH₂

O A750 CF₂Cl CH₂

O A751 CF₂Cl CH₂

O A752 CF₂Cl CH₂

O A753 CF₂Cl CH₂

O A754 CF₂Cl CH₂

O A755 CF₂Cl CH₂

O A756 CF₂Cl CH₂

O A757 CF₂Cl CH₂

O A758 CF₂Cl CH₂

O A759 CF₂Cl CH₂

O A760 CF₂Cl CH₂

O A761 CF₂Cl CH₂

O A762 CF₂Cl CH₂

O A763 CF₂Cl CH₂

O A764 CF₂Cl CH₂

O A765 CF₂Cl CH₂

O A766 CF₂Cl CH₂

O A767 CF₂Cl CH₂

O A768 CF₂Cl CH₂

O A769 CF₂Cl CH₂

O A770 CF₂Cl CH₂

O A771 CF₂Cl CH₂

O A772 CF₂Cl CH₂

O A773 CF₂Cl CH₂

O A774 CF₂Cl CH₂

O A775 CF₂Cl CH₂

O A776 CF₂Cl CH₂

O A777 CF₂Cl CH₂

O A778 CF₂Cl CH₂

O A779 CF₂Cl CH₂

O A780 CF₂Cl CH₂

O A781 CF₂Cl CH₂

O A782 CF₂Cl CH₂

O A783 CF₂Cl CH₂

O A784 CF₂Cl CH₂

O A785 CF₂Cl CH₂

O A786 CF₂Cl CH₂

O A787 CF₂Cl CH₂

O A788 CF₂Cl CH₂

O A789 CF₂Cl CH₂

O A790 CF₂Cl CH₂

O A791 CF₂Cl CH₂

O A792 CF₂Cl CH₂

O A793 CF₂Cl CH₂

O A794 CF₂Cl CH₂

O A795 CF₂Cl CH₂

O A796 CF₂Cl CH₂

O A797 CF₂Cl CH₂

O A798 CF₂Cl CH₂

O A799 CF₂Cl CH₂

O A800 CF₂Cl CH₂

O A801 CF₂Cl CH₂

O A802 CF₂Cl CH₂

O A803 CF₂Cl CH₂

O A804 CF₂Cl CH₂

O A805 CF₂Cl CH₂

O A806 CF₂Cl CH₂

O A807 CF₂Cl CH₂

O A808 CF₂Cl CH₂

O A809 CF₂Cl CH₂

O A810 CF₂Cl CH₂

O A811 CF₂Cl CH₂

O A812 CF₂Cl CH₂

O A813 CF₂Cl CH₂

O A814 CF₂Cl CH₂

O A815 CF₂Cl CH₂

O A816 CF₂Cl CH₂

O A817 CF₃ CH₂ CH₃SCH₂CH₂ O A818 CF₃ CH₂ CH₃SOCH₂CH₂ O A819 CF₃ CH₂ CH₃SO₂CH₂CH₂ O A820 CF₃ CH₂ CH₃OCH₂CH₂ O A821 CF₃ CH₂ CH₃OCH₂CH₂ O A822 CF₃ CH₂ CH₃OCH₂CH₂ O A823 CF₃ CH₂ CH₃OCH₂CH₂ O A824 CF₃ CH₂ CH₃OCH₂CH₂ O A825 CF₃ CH₂ CH₃OCH₂CH₂ S A826 CF₃ CH₂ CH₃OCH₂CH₂ SO A827 CF₃ CH₂ CH₃OCH₂CH₂ SO₂ A828 CF₃ CH₂ CH₃SO₂CH₂CH₂ O A829 CF₃ CH₂

S A830 CF₃ CH₂

S A831 CF₃ CH₂

S A832 CF₃ CH₂

S A833 CF₃ CH₂ CH₃C(O) O A834 CF₃ CH₂ CF₃CH₂ O A835 CF₃ CH₂ CH₃OCH₂CH₂OCH₂CH₂ O A836 CF₃ CH₂ HC≡CCH₂CH₂ O A837 CF₃ CH₂

O A838 CF₃ CH₂ CH₃CH₂C(OCH₃)HOCH₂CH₂ O A839 CF₃ CH₂ (CH₃)₃CC(O) O A840 CF₃ CH₂ CH₂═CHCH₂OCH₂CH₂ O A841 CF₃ CH₂ CH₃CH₂CH₂OCH₂CH₂ O A842 CF₃ CH₂

O A843 CF₃ CH₂ n-heptyl-C(O) O A844 CF₃ CH₂ phenyl-C(O) A845 CF₃ CH₂ CF₃CH₂OCH₂CH₂ O A846 CF₃ CH₂ CH₃OCH₂CH₂CH₂ O A847 CF₃ CH₂ HOCH₂CH₂CH₂ O A848 CF₃ CH₂

O A849 CF₃ CH₂ N≡CCH₂CH₂ O A850 CF₃ CH₂ ClCH₂CH₂ O A851 CF₃ CH₂

O A852 CF₃ CH₂

O A853 CF₃ CH₂ CH₃OCH₂C(Br)HCH₂ O A854 CF₃ CH₂

O A855 CF₃ CH₂

O A856 CF₃ CH₂ HOCH₂CH₂ O A857 CF₃ CH₂

O A858 CF₃ CH₂ CH₃(OCH₂CH₂)₃ O A859 CF₃ CH₂ CH₃CH₂OC(CH₃)HOCH₂CH₂ O A860 CF₃ CH₂ n-heptyl-C(O)OCH₂CH₂ O A861 CF₃ CH₂ CH₃C(O)OCH₂CH₂ O A862 CF₃ CH₂ CH₃SO₂OCH₂CH₂ O A863 CF₃ CH₂

O A864 CF₃ CH₂ CH₃ —N(CH₃)SO₂— A865 CF₃ CH₂ HOCH₂C(OH)HCH₂ O A866 CF₃ CH₂ phenyl-C(O)OCH₂CH₂ O A867 CF₃ CH₂ tert-butyl-C(O)OCH₂CH₂ O A868 CF₃ CH₂ CH₃OC(O)CH₂ O A869 CF₃ CH₂CH₂CH₂ CH₃ O A870 CF₃ CH₂CH₂CH₂ CH₂CH₃ O A871 CF₃ CH₂CH₂CH₂ CH₃ O A872 CF₃ CH₂CH₂CH₂ CH₂CH₃ O

The process according to the invention can be used especially advantageously for the preparation of the following compounds of Table 2:

In Table 2 which follows, the attachment position of the individual structures of the heterocycles of the group R₂ to the substituent R₁—X₁—, or to the C₁-C₄alkylene, C₂-C₄alkenyl-C₁-C₄alkylene, C₂-C₄alkynyl-C₁-C₄alkylene, —N(R₁₂)—C₁-C₄alkylene, —SO—C₁-C₄alkylene or —SO₂—C₁-C₄alkylene groups which connect the heterocycle of R₂ to the basic structure of formula I, is that nitrogen atom which is located at the same geometric position as is indicated in the Example below.

For example, the attachment position of the group

in the case of compound A 1.001 is the position indicated by an arrow:

The free valencies in those structures represent terminal CH₃ groups, as in the case of, for example, the structure

which may also be depicted as follows:

TABLE 2 Compounds of formula Ia wherein R is either methyl or ethyl: (Ia)

Comp. no. R₄ —R₁— —X₁—R₂ A1.001 CF₂Cl CH₂

A1.002 CF₂H CH₂

A1.003 CF₃ CH₂

A1.004 CF₃ CH₂OCH₂CH₂

A1.005 CF₂Cl CH₂OCH₂CH₂

A1.006 CHF₂ CH₂OCH₂CH₂

A1.007 CF₃ CH₂

A1.008 CF₂Cl CH₂

A1.009 CHF₂ CH₂

A1.010 CF₃ CH₂OCH₂CH₂

A1.011 CF₂Cl CH₂OCH₂CH₂

A1.012 CHF₂ CH₂OCH₂CH₂

A1.013 CF₃ CH₂

A1.014 CF₂Cl CH₂

A1.015 CHF₂ CH₂

A1.016 CF₃ CH₂OCH₂CH₂

A1.017 CF₂Cl CH₂OCH₂CH₂

A1.018 CHF₂ CH₂OCH₂CH₂

A1.019 CF₃ CH₂

A1.020 CF₂Cl CH₂

A1.021 CHF₂ CH₂

A1.022 CF₃ CH₂OCH₂CH₂

A1.023 CF₂Cl CH₂OCH₂CH₂

A1.024 CHF₂ CH₂OCH₂CH₂

A1.025 CF₃ CH₂

A1.026 CF₂Cl CH₂

A1.027 CHF₂ CH₂

A1.028 CF₃ CH₂OCH₂CH₂

A1.029 CF₂Cl CH₂OCH₂CH₂

A1.030 CHF₂ CH₂OCH₂CH₂

A1.031 CF₃ CH₂

A1.032 CF₂Cl CH₂

A1.033 CHF₂ CH₂

A1.034 CF₃ CH₂OCH₂CH₂

A1.035 CF₂Cl CH₂OCH₂CH₂

A1.036 CHF₂ CH₂OCH₂CH₂

A1.037 CF₃ CH₂

A1.038 CF₂Cl CH₂

A1.039 CHF₂ CH₂

A1.040 CF₃ CH₂OCH₂CH₂

A1.041 CF₂Cl CH₂OCH₂CH₂

A1.042 CHF₂ CH₂OCH₂CH₂

A1.043 CF₃ CH₂

A1.044 CF₂Cl CH₂

A1.045 CHF₂ CH₂

A1.046 CF₃ CH₂OCH₂CH₂

A1.047 CF₂Cl CH₂OCH₂CH₂

A1.048 CHF₂ CH₂OCH₂CH₂

A1.049 CF₃ CH₂

A1.050 CF₂Cl CH₂

A1.051 CHF₂ CH₂

A1.052 CF₃ CH₂OCH₂CH₂

A1.053 CF₂Cl CH₂OCH₂CH₂

A1.054 CHF₂ CH₂OCH₂CH₂

A1.055 CF₃ CH₂

A1.056 CF₂Cl CH₂

A1.057 CHF₂ CH₂

A1.058 CF₃ CH₂OCH₂CH₂

A1.059 CF₂Cl CH₂OCH₂CH₂

A1.060 CHF₂ CH₂OCH₂CH₂

A1.061 CF₃ CH₂

A1.062 CF₂Cl CH₂

A1.063 CHF₂ CH₂

A1.064 CF₃ CH₂OCH₂CH₂

A1.065 CF₂Cl CH₂OCH₂CH₂

A1.066 CHF₂ CH₂OCH₂CH₂

A1.067 CF₃ CH₂

A1.068 CF₂Cl CH₂

A1.069 CHF₂ CH₂

A1.070 CF₃ CH₂OCH₂CH₂

A1.071 CF₂Cl CH₂OCH₂CH₂

A1.072 CHF₂ CH₂OCH₂CH₂

A1.073 CF₃ CH₂

A1.074 CF₂Cl CH₂

A1.075 CHF₂ CH₂

A1.076 CF₃ CH₂OCH₂CH₂

A1.077 CF₂Cl CH₂OCH₂CH₂

A1.078 CHF₂ CH₂OCH₂CH₂

A1.079 CF₃ CH₂

A1.080 CF₂Cl CH₂

A1.081 CHF₂ CH₂

A1.082 CF₃ CH₂OCH₂CH₂

A1.083 CF₂Cl CH₂OCH₂CH₂

A1.084 CHF₂ CH₂OCH₂CH₂

A1.085 CF₃ CH₂

A1.086 CF₂Cl CH₂

A1.087 CHF₂ CH₂

A1.088 CF₃ CH₂OCH₂CH₂

A1.089 CF₂Cl CH₂OCH₂CH₂

A1.090 CHF₂ CH₂OCH₂CH₂

A1.091 CF₃ CH₂

A1.092 CF₂Cl CH₂

A1.093 CHF₂ CH₂

A1.094 CF₃ CH₂OCH₂CH₂

A1.095 CF₂Cl CH₂OCH₂CH₂

A1.096 CHF₂ CH₂OCH₂CH₂

A1.097 CF₃ CH₂

A1.098 CF₂Cl CH₂

A1.099 CHF₂ CH₂

A1.100 CF₃ CH₂OCH₂CH₂

A1.101 CF₂Cl CH₂OCH₂CH₂

A1.102 CHF₂ CH₂OCH₂CH₂

A1.103 CF₃ CH₂

A1.104 CF₂Cl CH₂

A1.105 CHF₂ CH₂

A1.106 CF₃ CH₂OCH₂CH₂

A1.107 CF₂Cl CH₂OCH₂CH₂

A1.108 CHF₂ CH₂OCH₂CH₂

A1.109 CF₃ CH₂

A1.110 CF₂Cl CH₂

A1.111 CHF₂ CH₂

A1.112 CF₃ CH₂OCH₂CH₂

A1.113 CF₂Cl CH₂OCH₂CH₂

A1.114 CHF₂ CH₂OCH₂CH₂

A1.115 CF₃ CH₂

A1.116 CF₂Cl CH₂

A1.117 CHF₂ CH₂

A1.118 CF₃ CH₂OCH₂CH₂

A1.119 CF₂Cl CH₂OCH₂CH₂

A1.120 CHF₂ CH₂OCH₂CH₂

A1.121 CF₃ CH₂

A1.122 CF₂Cl CH₂

A1.123 CHF₂ CH₂

A1.124 CF₃ CH₂OCH₂CH₂

A1.125 CF₂Cl CH₂OCH₂CH₂

A1.126 CHF₂ CH₂OCH₂CH₂

A1.127 CF₃ CH₂

A1.128 CF₂Cl CH₂

A1.129 CHF₂ CH₂

A1.130 CF₃ CH₂OCH₂CH₂

A1.131 CF₂Cl CH₂OCH₂CH₂

A1.132 CHF₂ CH₂OCH₂CH₂

A1.133 CF₃ CH₂

A1.134 CF₂Cl CH₂

A1.135 CHF₂ CH₂

A1.136 CF₃ CH₂OCH₂CH₂

A1.137 CF₂Cl CH₂OCH₂CH₂

A1.138 CHF₂ CH₂OCH₂CH₂

A1.139 CF₃ CH₂

A1.140 CF₂Cl CH₂

A1.141 CHF₂ CH₂

A1.142 CF₃ CH₂OCH₂CH₂

A1.143 CF₂Cl CH₂OCH₂CH₂

A1.144 CHF₂ CH₂OCH₂CH₂

A1.145 CF₃ CH₂

A1.146 CF₂Cl CH₂

A1.147 CHF₂ CH₂

A1.148 CF₃ CH₂OCH₂CH₂

A1.149 CF₂Cl CH₂OCH₂CH₂

A1.150 CHF₂ CH₂OCH₂CH₂

A1.151 CF₃ CH₂

A1.152 CF₂Cl CH₂

A1.153 CHF₂ CH₂

A1.154 CF₃ CH₂OCH₂CH₂

A1.155 CF₂Cl CH₂OCH₂CH₂

A1.156 CHF₂ CH₂OCH₂CH₂

A1.157 CF₃ CH₂

A1.158 CF₂Cl CH₂

A1.159 CHF₂ CH₂

A1.160 CF₃ CH₂OCH₂CH₂

A1.161 CF₂Cl CH₂OCH₂CH₂

A1.162 CHF₂ CH₂OCH₂CH₂

A1.163 CF₃ CH₂

A1.164 CF₂Cl CH₂

A1.165 CHF₂ CH₂

A1.166 CF₃ CH₂OCH₂CH₂

A1.167 CF₂Cl CH₂OCH₂CH₂

A1.168 CHF₂ CH₂OCH₂CH₂

A1.169 CF₃ CH₂

A1.170 CF₂Cl CH₂

A1.171 CHF₂ CH₂

A1.172 CF₃ CH₂OCH₂CH₂

A1.173 CF₂Cl CH₂OCH₂CH₂

A1.174 CHF₂ CH₂OCH₂CH₂

A1.175 CF₃ CH₂

A1.176 CF₂Cl CH₂

A1.177 CHF₂ CH₂

A1.178 CF₃ CH₂OCH₂CH₂

A1.179 CF₂Cl CH₂OCH₂CH₂

A1.180 CHF₂ CH₂OCH₂CH₂

A1.181 CF₃ CH₂

A1.182 CF₂Cl CH₂

A1.183 CHF₂ CH₂

A1.184 CF₃ CH₂OCH₂CH₂

A1.185 CF₂Cl CH₂OCH₂CH₂

A1.186 CHF₂ CH₂OCH₂CH₂

A1.187 CF₃ CH₂

A1.188 CF₂Cl CH₂

A1.189 CHF₂ CH₂

A1.190 CF₃ CH₂OCH₂CH₂

A1.191 CF₂Cl CH₂OCH₂CH₂

A1.192 CHF₂ CH₂OCH₂CH₂

A1.193 CF₃ CH₂

A1.194 CF₂Cl CH₂

A1.195 CHF₂ CH₂

A1.196 CF₃ CH₂OCH₂CH₂

A1.197 CF₂Cl CH₂OCH₂CH₂

A1.198 CHF₂ CH₂OCH₂CH₂

A1.199 CF₃ CH₂

A1.200 CF₂Cl CH₂

A1.201 CHF₂ CH₂

A1.202 CF₃ CH₂

A1.203 CF₂Cl CH₂

A1.204 CHF₂ CH₂

A1.205 CF₃ CH₂OCH₂CH₂

A1.206 CF₂Cl CH₂OCH₂CH₂

A1.207 CHF₂ CH₂OCH₂CH₂

A1.208 CF₃ CH₂

A1.209 CF₃ CH₂

A1.210 CHF₂ CH₂

A1.211 CF₃ CH₂

A1.212 CHF₂ CH₂

A1.213 CF₃ CH₂

A1.214 CF₂Cl CH₂

A1.215 CHF₂ CH₂

A1.216 CF₃ CH₂OCH₂CH₂

A1.217 CF₂Cl CH₂OCH₂CH₂

A1.218 CHF₂ CH₂OCH₂CH₂

A1.219 CF₃ CH₂

A1.220 CF₃ CH₂OCH₂CH₂

A1.221 CF₃ CH₂

A1.222 CF₃ CH₂

A1.223 CF₃ CH₂

A1.224 CF₃ CH₂

A1.225 CClF₂ CH₂

A1.226 CClF₂ CH₂

A1.227 CClF₂ CH₂

A1.228 CClF₂ CH₂

A1.229 CClF₂ CH₂

A1.230 CHF₂ CH₂

A1.231 CHF₂ CH₂

A1.232 CHF₂ CH₂

A1.233 CHF₂ CH₂

A1.234 CHF₂ CH₂

A1.235 CF₃ CH₂

A1.236 CHF₂ CH₂

A1.237 CF₃ CH₂

A1.238 CHF₂ CH₂

A1.240 CF₃ CH₂

A1.241 CHF₂ CH₂

A1.242 CF₃ CH₂

A1.243 CF₃ CH₂

A1.244 CF₃ CH₂

A1.245 CF₃ CH₂ 

1. A process for the preparation of a compound of formula I

wherein R is C₁-C₆alkyl; R₀₅ is Hydrogen, C₁-C₃alkyl, C₁-C₃haloalkyl or C₁-C₃alkyl-C₁-C₃alkoxy; R₁ is a C₁-C₆alkylene, C₃-C₆alkenylene or C₃-C₆alkynylene chain which may be substituted one or more times by halogen and/or by R₅, the unsaturated bonds of the chain not being attached directly to the substituent X₁; R₄ is C₁-C₄haloalkyl; X₁ is oxygen, —O(CO)—, —(CO)O—, —O(CO)O—, —N(R₆)—O—, —O—NR₁₇—, thio, sulfinyl, sulfonyl, —SO₂NR₇—, —NR₁₈SO₂—, —N(SO₂R_(18a))—, —N(R_(18b))C(O)— or —NR₈—; R_(18a) is C₁-C₆alkyl; R₂ is hydrogen or C₁-C₈alkyl, or is a C₁-C₈alkyl, C₃-C₆alkenyl or C₃-C₆alkynyl group which may be substituted one or more times by substituents selected from halogen, hydroxy, amino, formyl, nitro, cyano, mercapto, carbamoyl, C₁-C₆alkoxy, C₁-C₆alkoxycarbonyl, C₂-C₆alkenyl, C₂-C₆haloalkenyl, C₂-C₆alkynyl, C₂-C₆haloalkynyl, C₃-C₆cycloalkyl, halo-substituted C₃-C₆cycloalkyl, C₃-C₆alkenyloxy, C₃-C₆alkynyloxy, C₁-C₆haloalkoxy, C₃-C₆haloalkenyloxy, cyano-C₁-C₆alkoxy, C₁-C₆alkoxy-C₁-C₆alkoxy, C₁-C₆alkoxy-C₁-C₆alkoxy-C₁-C₆alkoxy, C₁-C₆alkylthio-C₁-C₆alkoxy, C₁-C₆alkylsulfinyl-C₁-C₆alkoxy, C₁-C₆alkylsulfonyl-C₁-C₆alkoxy, C₁-C₆alkoxycarbonyl-C₁-C₆alkoxy, C₁-C₆alkylcarbonyl, C₁-C₆alkylthio, C₁-C₆alkylsulfinyl, C₁-C₆alkylsulfonyl, C₁-₆haloalkylthio, C₁-C₆haloalkylsulfinyl, C₁-C₆haloalkylsulfonyl, oxiranyl (which may in turn be substituted by C₁-C₆alkyl), (3-oxetanyl)oxy (which may in turn be substituted by C₁-C₆alkyl), benzyloxy, benzylthio, benzylsulfinyl, benzylsulfonyl, C₁-C₆alkylamino, di(C₁-C₆alkyl)amino, R₉S(O)₂O—, R₁₀N(R₁₁)SO₂—, rhodano, phenyl, phenoxy, phenylthio, phenylsulfinyl and phenylsulfonyl; it being possible for the phenyl- or benzyl-containing groups to be in turn substituted by one or more C₁-C₆alkyl, C₁-C₆haloalkyl, C₁-C₆alkoxy, C₁-C₆haloalkoxy, halogen, cyano, hydroxy or nitro groups, or R₂ is phenyl which may be substituted one or more times by C₁-C₆alkyl, C₁-C₆haloalkyl, C₁-C₆alkoxy, C₁-C₆haloalkoxy, halogen, cyano, hydroxy or by nitro; or R₂ is C₃-C₆cycloalkyl, C₁-C₆alkoxy- or C₁-C₆alkyl-substituted C₃-C₆cycloalkyl, 3-oxetanyl or C₁-C₆alkyl-substituted 3-oxetanyl; or R₂ is a three- to ten-membered, monocyclic or fused bicyclic, ring system which may be aromatic, partially saturated or fully saturated and may contain from 1 to 4 hetero atoms selected from nitrogen, oxygen, sulfur, and/or may contain the group —C(═O)—, —C(═S)—, —C(═NR₁₉)—, —(N═O)—, —S(═O)— or —SO₂—, the ring system being attached to the substituent X₁ either directly or by way of a C₁-C₄alkylene, C₂-C₄alkenylene, C₂-C₄alkynylene, —N(R₁₂)—C₁-C₄alkylene, —O—C₁-C₄alkylene, —S—C₁-C₄alkylene, —SO—C₁-C₄alkylene or —SO₂—C₁-C₄alkylene group and each ring system containing no more than 2 oxygen atoms and no more than two sulfur atoms, and it being possible for each ring system itself to be substituted one or more times by C₁-C₆alkyl, C₁-C₆haloalkyl, C₂-C₆alkenyl, C₂-C₆haloalkenyl, C₂-C₆alkynyl, C₂-C₆haloalkynyl, C₁-C₆alkoxy, C₁-C₆haloalkoxy, C₃-C₆alkenyloxy, C₃-C₆alkynyloxy, mercapto, amino, hydroxy, C₁-C₆alkylthio, C₁-C₆haloalkylthio, C₃-C₆alkenylthio, C₃-C₆haloalkenylthio, C₃-C₆alkynylthio, C₁-C₃alkoxy-C₁-C₃alkylthio, C₁-C₄alkylcarbonyl-C₁-C₃alkylthio, C₁-C₄alkoxycarbonyl-C₁-C₃alkylthio, cyano-C₁-C₃alkylthio, C₁-C₆-alkylsulfinyl, C₁-C₆haloalkylsulfinyl, C₁-C₆alkylsulfonyl, C₁-C₆haloalkylsulfonyl, aminosulfonyl, C₁-C₂alkylaminosulfonyl, N,N-di(C₁-C₂alkyl)aminosulfonyl, di(C₁-C₄alkyl)amino, halogen, cyano, nitro or by phenyl, it being possible for the phenyl group to be in turn substituted by hydroxy, C₁-C₆alkylthio, C₁-C₆haloalkylthio, C₃-C₆alkenylthio, C₃-C₆haloalkenylthio, C₃-C₆alkynylthio, C₁-C₃alkoxy-C₁-C₃alkylthio, C₁-C₄alkylcarbonyl-C₁-C₃alkylthio, C₁-C₄alkoxycarbonyl-C₁-C₃alkylthio, cyano-C₁-C₃alkylthio, C₁-C₆alkylsulfinyl, C₁-C₆haloalkylsulfinyl, C₁-C₆alkylsulfonyl, C₁-C₆haloalkylsulfonyl, aminosulfonyl, C₁-C₂alkylaminosulfonyl, N,N-di(C₁-C₂alkyl)aminosulfonyl, di(C₁-C₄alkyl)amino, halogen, cyano or by nitro, and the substituents on nitrogen in a heterocyclic ring being other than halogen; R₅ is hydroxy, C₁-C₆alkoxy, C₃-C₆cycloalkyloxy, C₁-C₆alkoxy-C₁-C₆alkoxy, C₁-C₆alkoxy-C₁-C₆alkoxy-C₁-C₆alkoxy or C₁-C₂alkylsulfonyloxy; R₆, R₇, R₈, R₉, R₁₀ R₁₁, R₁₂, R₁₇, R₁₈ and R_(18b) are each independently of the others hydrogen, C₁-C₆alkyl, C₁-C₆haloalkyl, C₁-C₆alkoxycarbonyl, C₁-C₆alkylcarbonyl, C₁-C₆-alkoxy-C₁-C₆alkyl, C₁-C₆alkoxy-C₁-C₆alkyl substituted by C₁-C₆alkoxy, benzyl, or phenyl, it being possible for phenyl and benzyl to be in turn substituted one or more times by C₁-C₆alkyl, C₁-C₆haloalkyl, C₁-C₆alkoxy, C₁-C₆haloalkoxy, halogen, cyano, hydroxy or by nitro; R₆ not being hydrogen when R₉ is hydrogen, C₁-C₆alkoxycarbonyl or C₁-C₆alkylcarbonyl; or the group —R₁—X₁—R₂ together is C₁-C₆alkyl, C₂-C₆alkenyl, C₂-C₆haloalkenyl, C₂-C₆-alkynyl, C₂-C₆haloalkynyl, C₃-C₆cycloalkyl, C₁-C₆alkoxy, C₁-C₆haloalkoxy, C₁-C₆alkylthio, C₁-C₆alkylsulfinyl, C₁-C₆alkylsulfonyl, C₁-C₆haloalkyl, C₁-C₆haloalkylthio, C₁-C₆haloalkylsulfinyl, C₁-C₆haloalkylsulfonyl, C₁-C₆alkoxycarbonyl, C₁-C₆alkylcarbonyl, C₁-C₆alkylamino, di(C₁-C₆alkyl)amino, C₁-C₆alkylaminosulfonyl, di(C₁-C₆alkyl)aminosulfonyl, —NH—S—R₁₃, —N—(C₁-C₄alkylthio)-R₁₃, —NH—SO—R₁₄, —N—(C₁-C₄alkylsulfonyl)-R₁₄, —NH—SO₂—R₁₅, —N—(C₁-C₄alkylsulfonyl)-R₁₅, nitro, cyano, halogen, hydroxy, amino, formyl, rhodano-C₁-C₆alkyl, cyano-C₁-C₆alkyl, oxiranyl, C₃-C₆alkenyloxy, C₃-C₆alkynyloxy, C₁-C₆alkoxy-C₁-C₆alkoxy, cyano-C₁-C₆alkenyloxy, C₁-C₆alkoxycarbonyloxy-C₁-C₆alkoxy, C₃-C₆alkynyloxy, cyano-C₁-C₆alkoxy, C₁-C₆alkoxycarbonyl-C₁-C₆alkoxy, C₁-C₆alkylthio-C₁-C₆alkoxy, C₁-C₆alkoxycarbonyl-C₁-C₆alkylthio, C₁-C₆alkoxycarbonyl-C₁-C₆alkylsulfinyl, C₁-C₆alkoxycarbonyl-C₁-C₆-alkylsulfonyl, C₁-C₆alkylsulfonyloxy, C₁-C₆haloalkylsulfonyloxy, phenyl, benzyl, phenoxy, phenylthio, phenylsulfinyl, phenylsulfonyl, benzylthio, benzylsulfinyl or benzylsulfonyl, it being possible for the phenyl groups to be substituted one or more times by halogen, methyl, ethyl, trifluoromethyl, methoxy or by nitro; or the group —R₁—X₁—R₂ together is a three- to ten-membered, monocyclic or fused bicyclic, ring system, which may be aromatic, partially saturated or saturated and which may contain from 1 to 4 hetero atoms selected from nitrogen, oxygen and sulfur and/or may contain one or two groups selected from —C(═O)—, —C(═S)—, —C(═NR₂O)—, —(N═O)—, —S(═O)— and —SO₂—, the ring system either being attached to the pyridine ring directly via a carbon atom or being attached to the pyridine ring via a carbon atom or via a nitrogen atom by way of a C₁-C₄alkylene, C₂-C₄alkenyl or C₂-C₄alkynyl chain, and it being possible for each ring system to contain no more than 2 oxygen atoms and no more than two sulfur atoms, and it being possible for the ring system itself to be substituted one, two or three times by substituents selected from C₁-C₆alkyl, C₁-C₆haloalkyl, C₃-C₆alkenyl, C₃-C₆haloalkenyl, C₃-C₆alkynyl, C₃-C₆haloalkynyl, C₃-C₆-cycloalkyl, hydroxy, C₁-C₆alkoxy, C₁-C₆haloalkoxy, C₃-C₆alkenyloxy, C₃-C₆alkynyloxy, mercapto, C₁-C₆alkylthio, C₁-C₆haloalkylthio, C₃-C₆alkenylthio, C₃-C₆haloalkenylthio, C₃-C₆alkynylthio, C₁-C₃alkoxy-C₁-C₃alkylthio, C₁-C₃alkylcarbonyl-C₁-C₃alkylthio, C₁-C₄alkoxycarbonyl-C₁-C₃alkylthio, cyano-C₁-C₃alkylthio, C₁-C₆alkylsulfinyl, C₁-C₆-haloalkylsulfinyl, C₁-C₆alkylsulfonyl, C₁-C₆haloalkylsulfonyl, aminosulfonyl, C₁-C₂alkylaminosulfonyl, di(C₁-C₆alkyl)aminosulfonyl, C₁-C₃alkylene-R₁₆, amino, C₁-C₆alkylamino, C₁-C₆alkoxyamino, di(C₁-C₆alkyl)amino, (N—C₁-C₆alkyl)-C₁-C₆alkoxyamino, halogen, cyano, nitro, phenyl, benzyloxy and benzylthio, it being possible for phenyl, benzyloxy and benzylthio to be in turn substituted on the phenyl ring by C₁-C₃alkyl, C₁-C₃haloalkyl, C₁-C₃alkoxy, C₁-C₃haloalkoxy, halogen, cyano or by nitro, and substituents on a nitrogen atom in a heterocyclic ring being other than halogen; R₁₃ is N(H)—C₁-C₆alkyl, N(H)—C₁-C₆alkoxy, N—(C₁-C₆alkyl)-C₁-C₆alkyl, N—(C₁-C₆alkyl)-C₁-C₆alkoxy, C₁-C₆alkoxy, C₁-C₆haloalkoxy, C₁-C₆alkyl, C₁-C₆haloalkyl, C₃-C₆alkenyl, C₃-C₆haloalkenyl, C₃-C₆alkynyl, C₃-C₆haloalkynyl, C₃-C₆cycloalkyl or phenyl, it being possible for phenyl to be in turn substituted by C₁-C₃alkyl, C₁-C₃haloalkyl, C₁-C₃alkoxy, C₁-C₃haloalkoxy, halogen, cyano or by nitro; R₁₄ is N(H)—C₁-C₆alkyl, N(H)—C₁-C₆alkoxy, N—(C₁-C₆alkyl)-C₁-C₆alkyl, N—(C₁-C₆alkyl)-C₁-C₆alkoxy, C₁-C₆alkoxy, C₁-C₆haloalkoxy, C₁-C₆alkyl, C₁-C₆haloalkyl, C₃-C₆alkenyl, C₃-C₆haloalkenyl, C₃-C₆alkynyl, C₃-C₆haloalkynyl, C₃-C₆cycloalkyl or phenyl, it being possible for phenyl to be in turn substituted by C₁-C₃alkyl, C₁-C₃haloalkyl, C₁-C₃alkoxy, C₁-C₃haloalkoxy, halogen, cyano or by nitro; R₁₅ is N(H)—C₁-C₆alkyl, N(H)—C₁-C₆alkoxy, N—(C₁-C₆alkyl)-C₁-C₆alkyl, N—(C₁-C₆alkyl)-C₁-C₆alkoxy, C₁-C₆alkoxy, C₁-C₆haloalkoxy, C₁-C₆alkyl, C₁-C₆haloalkyl, C₃-C₆alkenyl, C₃-C₆haloalkenyl, C₃-C₆alkynyl, C₃-C₆haloalkynyl, C₃-C₆cycloalkyl or phenyl, it being possible for phenyl to be in turn substituted by C₁-C₃alkyl, C₁-C₃haloalkyl, C₁-C₃alkoxy, C₁-C₃haloalkoxy, halogen, cyano or by nitro; R₁₆ is C₁-C₃alkoxy, C₂-C₄alkoxycarbonyl, C₁-C₃alkylthio, C₁-C₃alkylsulfinyl, C₁-C₃alkylsulfonyl or phenyl, it being possible for phenyl to be in turn substituted by C₁-C₃alkyl, C₁-C₃haloalkyl, C₁-C₃alkoxy, C₁-C₃haloalkoxy, halogen, cyano or by nitro; and R₁₉ and R₂₀ are each independently of the other hydrogen, hydroxy, C₁-C₆alkyl, C₁-C₆haloalkyl, C₁-C₆alkoxy, cyano, C₁-C₆alkylcarbonyl, C₁-C₆alkoxycarbonyl or C₁-C₆alkylsulfonyl; which process comprises reacting a compound of formula II

wherein R₃ is C₁-C₈alkyl or C₃-C₆cycloalkyl and R₄ and R₀₅ are as defined for formula I, with a compound of formula III

wherein R, R₁, R₂ and X₁ are as defined for formula I, in an inert solvent in the presence of a proton source.
 2. A process according to claim 1, wherein there is prepared a compound of formula I wherein R₄ is halomethyl or haloethyl; R₀₅ is hydrogen; X₁ is oxygen, —O(CO)—, —(CO)O—, —O(CO)O—, —N(R₆)—O—, —O—NR₁₇—, thio, sulfinyl, sulfonyl, —SO₂NR₇—, —NR₁₈SO₂— or —NR₈—; R₂ is hydrogen or C₁-C₈alkyl, or a C₁-C₈alkyl, C₃-C₆alkenyl or C₃-C₆alkynyl group which is substituted one or more times by halogen, hydroxy, amino, formyl, nitro, cyano, mercapto, carbamoyl, C₁-C₆alkoxy, C₁-C₆alkoxycarbonyl, C₂-C₆alkenyl, C₂-C₆haloalkenyl, C₂-C₆alkynyl, C₂-C₆haloalkynyl, C₃-C₆cycloalkyl, halo-substituted C₃-C₆cycloalkyl, or by C₃-C₆alkenyloxy, C₃-C₆alkynyloxy, C₁-C₆haloalkoxy, C₃-C₆haloalkenyloxy, cyano-C₁-C₆alkoxy, C₁-C₆alkoxy-C₁-C₆alkoxy, C₁-C₆alkoxy-C₁-C₆alkoxy-C₁-C₆alkoxy, C₁-C₆alkylthio-C₁-C₆alkoxy, C₁-C₆alkylsulfinyl-C₁-C₆alkoxy, C₁-C₆alkylsulfonyl-C₁-C₆alkoxy, C₁-C₆alkoxycarbonyl-C₁-C₆alkoxy, C₁-C₆alkoxycarbonyl, C₁-C₆alkylcarbonyl, C₁-C₆alkylthio, C₁-C₆alkylsulfinyl, C₁-C₆alkylsulfonyl, C₁-C₆haloalkylthio, C₁-C₆haloalkylsulfinyl, C₁-C₆haloalkylsulfonyl, oxiranyl (which may in turn be substituted by C₁-C₆alkyl), or by (3-oxetanyl)oxy (which may in turn be substituted by C₁-C₆alkyl), or by benzylthio, benzylsulfinyl, benzylsulfonyl, C₁-C₆alkylamino, di(C₁-C₆alkyl)amino, R₉S(O)₂O—, R₁₀N(R₁₁)SO₂—, rhodano, phenyl, phenoxy, phenylthio, phenylsulfinyl or by phenylsulfonyl; it being possible for the phenyl- or benzyl-containing groups to be in turn substituted by one or more C₁-C₆alkyl, C₁-C₆haloalkyl, C₁-C₆alkoxy, C₁-C₆haloalkoxy, halogen, cyano, hydroxy or nitro groups, or R₂ is phenyl which may be substituted one or more times by C₁-C₆alkyl, C₁-C₆haloalkyl, C₁-C₆alkoxy, C₁-C₆haloalkoxy, halogen, cyano, hydroxy or by nitro; or R₂ is C₃-C₆cycloalkyl, C₁-C₆alkoxy- or C₁-C₆alkyl-substituted C₃-C₆cycloalkyl, 3-oxetanyl or C₁-C₆alkyl-substituted 3-oxetanyl; or R₂ is a five- to ten-membered, monocyclic or fused bicyclic, ring system which may be aromatic, partially saturated or fully saturated and may contain from 1 to 4 hetero atoms selected from nitrogen, oxygen, sulfur, and/or may contain the group —C(═O)—, —C(═S)—, —C(═NR₁₉)—, —(N═O)—, —S(═O)— or —SO₂—, the ring system being attached to the substituent X₁ directly or by way of a C₁-C₄alkylene, C₂-C₄alkenyl-C₁-C₄alkylene, C₂-C₄alkynyl-C₁-C₄alkylene, —N(R₁₂)—C₁-C₄alkylene, —SO—C₁-C₄alkylene or —SO₂—C₁-C₄alkylene group and each ring system containing no more than 2 oxygen atoms and no more than two sulfur atoms, and it being possible for each ring system itself to be substituted one or more times by C₁-C₆alkyl, C₁-C₆haloalkyl, C₂-C₆alkenyl, C₂-C₆haloalkenyl, C₂-C₆alkynyl, C₂-C₆haloalkynyl, C₁-C₆alkoxy, C₁-C₆haloalkoxy, C₃-C₆alkenyloxy, C₃-C₆alkynyloxy, mercapto, amino, hydroxy, C₁-C₆alkylthio, C₁-C₆haloalkylthio, C₃-C₆alkenylthio, C₃-C₆haloalkenylthio, C₃-C₆alkynylthio, C₁-C₃alkoxy-C₁-C₃alkylthio, C₁-C₄alkylcarbonyl-C₁-C₃alkylthio, C₁-C₄alkoxycarbonyl-C₁-C₃alkylthio, cyano-C₁-C₃alkylthio, C₁-C₆alkylsulfinyl, C₁-C₆haloalkylsulfinyl, C₁-C₆alkylsulfonyl, C₁-C₆haloalkylsulfonyl, aminosulfonyl, C₁-C₂alkylaminosulfonyl, N,N-di(C₁-C₂alkyl)aminosulfonyl, di(C₁-C₄alkyl)amino, halogen, cyano, nitro or by phenyl, it being possible for the phenyl group to be in turn substituted by hydroxy, C₁-C₆alkylthio, C₁-C₆haloalkylthio, C₃-C₆alkenylthio, C₃-C₆haloalkenylthio, C₃-C₆alkynylthio, C₁-C₃alkoxy-C₁-C₃alkylthio, C₁-C₄alkylcarbonyl-C₁-C₃alkylthio, C₁-C₄alkoxycarbonyl-C₁-C₃alkylthio, cyano-C₁-C₃alkylthio, C₁-C₆alkylsulfinyl, C₁-C₆haloalkylsulfinyl, C₁-C₆alkylsulfonyl, C₁-C₆haloalkylsulfonyl, aminosulfonyl, C₁-C₂alkylaminosulfonyl, N,N-di(C₁-C₂alkyl)aminosulfonyl, di(C₁-C₄alkyl)amino, halogen, cyano or by nitro, and the substituents on nitrogen in a heterocyclic ring being other than halogen; R₆, R₇, R₈, R₉, R₁₀ R₁₁, R₁₂, R₁₇ and R₁₈ are each independently of the others hydrogen, C₁-C₆alkyl, C₁-C₆haloalkyl, C₁-C₆alkoxycarbonyl, C₁-C₆alkylcarbonyl, C₁-C₆alkoxy-C₁-C₆alkyl, C₁-C₆alkoxy-C₁-C₆alkyl substituted by C₁-C₆alkoxy, benzyl, or phenyl, it being possible for phenyl and benzyl to be in turn substituted one or more times by C₁-C₆alkyl, C₁-C₆haloalkyl, C₁-C₆alkoxy, C₁-C₆haloalkoxy, halogen, cyano, hydroxy or by nitro; R₆ not being hydrogen when R₉ is hydrogen, C₁-C₆alkoxycarbonyl or C₁-C₆alkylcarbonyl; or the group —R₁—X₁—R₂ together is C₁-C₆alkyl, C₂-C₆alkenyl, C₂-C₆haloalkenyl, C₂-C₆-alkynyl, C₂-C₆haloalkynyl, C₃-C₆cycloalkyl, C₁-C₆alkoxy, C₁-C₆haloalkoxy, C₁-C₆alkylthio, C₁-C₆alkylsulfinyl, C₁-C₆alkylsulfonyl, C₁-C₆haloalkyl, C₁-C₆haloalkylthio, C₁-C₆haloalkylsulfinyl, C₁-C₆haloalkylsulfonyl, C₁-C₆alkoxycarbonyl, C₁-C₆alkylcarbonyl, C₁-C₆alkylamino, di(C₁-C₆alkyl)amino, C₁-C₆alkylaminosulfonyl, di(C₁-C₆alkyl)aminosulfonyl, —NH—S—R₁₃, —N—(C₁-C₄alkylthio)-R₁₃, —NH—SO—R₁₄, —N—(C₁-C₄alkylsulfonyl)-R₁₄, —NH—SO₂—R₁₅, —N—(C₁-C₄alkylsulfonyl)-R₁₅, nitro, cyano, halogen, hydroxy, amino, formyl, rhodano-C₁-C₆alkyl, cyano-C₁-C₆alkyl, oxiranyl, C₃-C₆alkenyloxy, C₃-C₆alkynyloxy, C₁-C₆alkoxy-C₁-C₆alkoxy, cyano-C₁-C₆alkenyloxy, C₁-C₆alkoxycarbonyloxy-C₁-C₆alkoxy, C₃-C₆alkynyloxy, cyano-C₁-C₆alkoxy, C₁-C₆alkoxycarbonyl-C₁-C₆alkoxy, C₁-C₆alkylthio-C₁-C₆alkoxy, alkoxycarbonyl-C₁-C₆alkylthio, alkoxycarbonyl-C₁-C₆alkylsulfinyl, alkoxycarbonyl-C₁-C₆alkylsulfonyl, C₁-C₆alkylsulfonyloxy, C₁-C₆haloalkylsulfonyloxy, phenyl, benzyl, phenoxy, phenylthio, phenylsulfinyl, phenylsulfonyl, benzylthio, benzylsulfinyl or benzylsulfonyl, it being possible for the phenyl groups to be substituted one or more times by halogen, methyl, ethyl, trifluoromethyl, methoxy or by nitro; or the group —R₁—X₁—R₂ together is a five- to ten-membered, monocyclic or fused bicyclic, ring system, which may be aromatic or partially saturated and which may contain from 1 to 4 hetero atoms selected from nitrogen, oxygen and sulfur, the ring system either being directly attached to the pyridine ring or being attached to the pyridine ring by way of a C₁-C₄alkylene group, and it being possible for each ring system to contain no more than 2 oxygen atoms and no more than two sulfur atoms, and/or to contain the group —C(═O)—, —C(═S)—, —C(═NR₂O)—, —(N═O)—, —S(═O)— or —SO₂—; and the ring system itself may be substituted one, two or three times by C₁-C₆alkyl, C₁-C₆haloalkyl, C₃-C₆alkenyl, C₃-C₆haloalkenyl, C₃-C₆alkynyl, C₃-C₆haloalkynyl, C₁-C₆alkoxy, C₁-C₆haloalkoxy, C₃-C₆alkenyloxy, C₃-C₆alkynyloxy, mercapto, C₁-C₆alkylthio, C₁-C₆haloalkylthio, C₃-C₆alkenylthio, C₃-C₆haloalkenylthio, C₃-C₆alkynylthio, C₂-C₅alkoxyalkylthio, C₃-C₅acetylalkylthio, C₃-C₆alkoxycarbonylalkylthio, C₂-C₄cyanoalkylthio, C₁-C₆alkylsulfinyl, C₁-C₆haloalkylsulfinyl, C₁-C₆alkylsulfonyl, C₁-C₆haloalkylsulfonyl, aminosulfonyl, C₁-C₂alkylaminosulfonyl, C₂-C₄dialkylaminosulfonyl, C₁-C₃alkylene-R₁₆, N(H)—C₁-C₆alkyl, N(H)—C₁-C₆alkoxy, N—(C₁-C₆alkyl)-C₁-C₆alkyl, N—(C₁-C₆alkyl)-C₁-C₆alkoxy, halogen, cyano, nitro, phenyl and by benzylthio, it being possible for phenyl and benzylthio to be in turn substituted on the phenyl ring by C₁-C₃alkyl, C₁-C₃haloalkyl, C₁-C₃alkoxy, C₁-C₃haloalkoxy, halogen, cyano or by nitro, and substituents on nitrogen in a heterocyclic ring being other than halogen; and R₁₉ and R₂₀ are each independently of the other hydrogen, hydroxy, C₁-C₆alkyl, C₁-C₆-haloalkyl, C₁-C₆alkoxy, C₁-C₆alkylcarbonyl, C₁-C₆alkoxycarbonyl or C₁-C₆alkylsulfonyl.
 3. A compound of formula IIIa

wherein R is as defined for formula I in claim
 1. 4. (canceled) 